Borate photoinitiators from polyboranes

ABSTRACT

Compounds of the formula I ##STR1## in which n and o are a number from 0 to 50, m is a number from 1 to 50, u and v are 0 or 1, and at least one of the indices u and v is 1, R 1 , R 2 , R 2a , R 3  and R 4  independently of one another are, for example, aromatic hydrocarbons, R 5 , if n and o are 0, is for example C 1  -C 12  alkyl and, if n and/or o are greater than 0, or if n and o are 0 and at the same time only one index u or v is 1, R 5  may additionally, for example, be an aromatic hydrocarbon, at least one of the radicals R 1 , R 2 , R 2a , R 3 , R 4  and R 5  being an aromatic hydrocarbon radical which is sterically hindered ortho to the boron atom, X is, for example, C 1  -C 20  alkylene, phenylene, biphenylene, etc., and Z is a radical which is able to form positive ions, are suitable as photoinitiators, both the compounds per se and their combination with dyes or other electron acceptors. Furthermore, the polyborane precursors of these borates possess, together with borate salts, photoinitiating properties.

The invention relates to mono- and polyborate compounds derived frompolyboranes, to their use as photoinitiators, alone and in combinationwith coinitiators or electron acceptors respectively, to the use ofpolyboranes in combination with coinitiators or electron donors asphotoinitiators, and to photopolymerizable compositions comprising thenovel photoinitiators.

Monoborate compounds in association with ionic dyes have been describedin the prior art as photoinitiators. For example, U.S. Pat. Nos.4,772,530, 4,772,541 and 5,151,520 disclose monocyclic triaryl alkylborate anions with catonic dyes, for example cyanines, rhodamines, etc.,as counterions. These compounds are employed as photoinitiators. In U.S.Pat. No. 4,954,414, cationic transition metal complexes are usedtogether with triaryl alkyl borate anions in photopolymerizablecompositions. From U.S. Pat. No. 5,055,372 it is also known to usequaternary ammonium compounds, for example tetramethylammonium,pyridinium, cetylpyridinium, etc., as cationic counterions to thetriaryl alkyl borate. In this publication, the borates are employed inassociation with aromatic ketone initiator compounds in photocurablematerials. In Z. Chem. 6 (1966), 34, H. Holzapfel, P. Nenning and O.Wildner describe the preparation of the sodium phenyl borate of1,4-bis(diphenylboryl)benzene. In Z. Chem. 6 (1966), 435, H. Holzapfel,P. Nenning and H. Stirn disclose the preparation of the correspondingbisphenyl borates and the corresponding naphthyl-substituted compounds.U.S. Pat. No. 3,311,662 describes polyborates which are employed asfungicides and bactericides. None of these documents disclosespolyborate compounds as photoinitiators.

For the extensive range of applications of photoinitiators, there is aneed in industry for reactive compounds. In the photocuring techniqueswhich employ borate compounds and have been disclosed to date, in theprior art, the addition of dyes or coinitiators is an absolutenecessity. However, there is particular interest in compounds which aresuitable alone as such initiators, with the result that the addition ofcoinitiators is not absolutely necessary.

It has now surprisingly been found that compounds of the formula I##STR2## in which n and o are each a number from 0 to 50; m is a numberfrom 1 to 50;

u and v are 0 or 1, and at least one of the indices u and v is 1;

R₁, R₂, R_(2a), R₃ and R₄ independently of one another are phenyl oranother aromatic hydrocarbon, which radicals are unsubstituted or aresubstituted by unsubstituted or halo-, OR₆ -- and/or NR₈ R₉ -substitutedC₁ -C₆ alkyl, OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉,C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen;

p is 0, 1 or 2;

q is 0 or 1;

R₅, is C₁ -C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C₂ -C₈ alkenyl, phenyl-C₁ -C₆alkyl or naphthyl-C₁ -C₃ alkyl, the radicals C₁ -C₁₂ alkyl, C₃ -C₁₂cycloalkyl, C₂ -C₈ alkenyl, phenyl-C₁ -C₆ alkyl or naphthyl beingunsubstituted or substituted by OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉,C(O)OR₆, C(O)NR₈ R₉, C(O)OR₁₀, ##STR3## SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ orhalogen, or R₅ is phenyl or another aromatic hydrocarbon radical, whichradicals are unsubstituted or substituted by C₁ -C₆ alkyl, OR₆, S(O)_(p)R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄R₁₅ or halogen, at least one of the radicals R₁, R₂, R_(2a), R₃, R₄ andR₅ being a phenyl radical which is substituted ortho to the bond to theboron atom, or being another aromatic hydrocarbon radical which issterically hindered ortho to the boron atom;

R₆ and R₇ are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- orhalo-substituted C₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substituted phenyl, or unsubstitutedor mono- to penta-C₁ -C₆ alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substitutedphenyl-C₁ -C₆ alkyl;

R_(7a) is C₁ -C₁₂ alkyl

R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ independently of one another areas defined for R₆ or are C₃ -C₁₂ cycloalkyl, or R₈ and R₉, together withthe N atom to which they are attached, form a 5- or 6-membered ringwhich may additionally contain O or S atoms, or R₁₄ and R₁₅, togetherwith the B atom to which they are attached, form a 5- or 6-memberedring;

X is C₁ -C₂₀ alkylene which is unsubstituted or substituted by OR₆,S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂R₁₃, BR₁₄ R₁₅, halogen or P(O)_(q) R₁₆ R₁₇, or X is C₃ -C₁₂cycloalkylene or C₂ -C₈ alkenylene, each of which is unsubstituted orsubstituted by OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉,C(O)R₁₀, Sir₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ or halogen, or where these radicals areinterrupted by one or more groups --O--, --S(O)_(p) -- or --NR₁₈ --, orX is a divalent aromatic hydrocarbon radical which is unsubstituted orsubstituted by C₁ -C₆ alkyl, OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉,C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ or halogen, or Xis C₁ -C₂₀ alkylene which is interrupted by one or more groups --O--,--S(O)_(p) -- or --NR₁₈ --, or X is a radical of the formula II or III##STR4## R₁₆ and R₁₇ independently of one another are as defined for R₆or are C₃ -C₁₂ cycloalkyl,

R₁₈ is as defined for R₆ or is hydrogen;

Y is --(CH₂)_(r) --, --C(O)--, --NR₁₈ --, --O--, --S(O)_(p) --, --CR₁₉R₂₀ --, ##STR5## r is 1, 2 or 3; s is 2 or 3;

R₁₉ and R₂₀ are C₁ -C₆ alkyl or phenyl, or R₁₉ and R₂₀, together withthe C atom to which they are attached, form a 5- or 6-membered ring;

A and Q independently of one another are a direct bond, --(CH₂)_(r) --,--CH═CH--, --C(O)--, --NR₁₈ --, --S(O)_(p) --, --CR₁₉ R₂₀ --, ##STR6##or the radicals R₁, R₂, R₃, R₄ and X form bridges to produce radicals ofthe formula (IV) or (V) ##STR7## G is --(CH₂)_(t) --, --CHCH--,--C(O)--, --NR₁₈ --, --O--, --S(O)_(p) --, --CR₁₉ R₂₀ --, ##STR8## t is0, 1 or 2; the radicals of the formulae (II), (III), (IV) and (V) beingunsubstituted or being substituted on the aromatic rings by OR₆,S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂R₁₃, BR₁₄ R₁₅ or halogen and where additional phenyl rings may be fusedto the phenyl rings of the formulae (II), (III), (IV) and (V); providedthat R₁, R_(2a), R₃ and R₄ are not simultaneously α-naphthyl, if X isphenylene or 4,4'-biphenylene; and

Z is a radical which is able to form positive ions, especially alkalimetals, ammonium or tetraalkylammonium, sulfonium- or phosphomiumradicals, are suitable as photoinitiators for the photopolymerization ofcompounds containing ethylenically unsaturated double bonds. Thecompounds of the formula I are per se surprisingly effective asphotoinitiators even without additional coinitiators.

In the borate compounds of the formula I, at least one of the radicalsR₁ -R₅ is a phenyl ring which is substituted ortho to the bond to theboron atom or is another aromatic hydrocarbon radical which issterically hindered ortho to the boron atom. Ortho-substitution here isgenerally understood to mean a bond in the o position of the aryl ringwith respect to the boron central atom, thus including, for example, afused-on ring. In accordance with this definition, therefore, somepolycyclic aromatic hydrocarbons, for example naphthyl, are also rings(ring systems) which are substituted ortho to the bond to the boroncentral atom.

Aromatic hydrocarbons as may be present in the novel compounds may, forexample, contain one or more, especially 1 or 2, heteroatoms. Examplesof suitable heteroatoms are N, P, O and S, preferably N or O. Examplesof aromatic hydrocarbon radicals are phenyl, α- and β-naphthyl,stilbenyl, biphenyl, o-, m-, p-terphenyl, triphenylphenyl, binaphthyl,anthracyl, phenanthryl, pyrenyl, furan-2-yl or furan-3-yl, thiophen-2-ylor thiophen-3-yl, pyridin-2-yl or pyridin-3-yl, quinolyl or isoquinolyl.

Also suitable are aromatic hydrocarbon radicals of the formula ##STR9##in which A₁ and A₂ independently of one another are a direct bond,--(CH₂)_(r) --, --CH═CH--, --C(O)--, NR₁₈, S(O)_(p), --CR₁₉ R₂₀,##STR10## where r, s, p, R₁₉ and R₂₀ are as defined above. Examples ofthese are anthracyl, fluorenyl, thianthryl, xanthyl, acridinyl,phenazinyl, phenothiazinyl, phenoxathiinyl and phenoxazinyl. ##STR11##

Substituted radicals phenyl, stilbenyl, biphenyl, o-, m- andp-terphenyl, triphenylphenyl, naphthyl, binaphthyl, anthracyl,phenanthryl, pyrenyl, ferrocenyl, furanyl, thiophenyl, pyridinyl,quinolinyl or isoquinolinyl are substituted one to four times, forexample one, two or three times, especially two or three times.Substituents on the phenyl ring are preferably in positions 2 or in 2,6or 2,4,6 configuration on the phenyl ring.

C₁ -C₁₂ Alkyl is linear or branched and is, for example, C_(1-C) ₈ -, C₁-C₆ - or C₁ -C₄ alkyl. Examples are methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl,2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl and dodecyl. R₅-R₁₅ are, for example, C₁ -C₈ alkyl, especially C₁ -C₆ alkyl, preferablyC₁ -C₄ alkyl.

C₃ -C₁₂ Cycloalkyl is for example cyclopropyl, cyclopentyl, cyclohexyl,cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl,preferably cyclohexyl.

C₂ -C₈ Alkenyl radicals may be mono or polyunsaturated and are forexample allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl,2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7-octenyl, especially allyl.

Phenyl-C₁ -C₆ alkyl is for example benzyl, phenylethyl, α-methylbenzyl,phenylpentyl, phenylhexyl or α,α-dimethylbenzyl, especially benzyl.Substituted phenyl-C₁ -C₅ alkyl is substituted one to four times, forexample once, twice or three times, especially twice or three times, onthe phenyl ring.

Naphthyl-C₁ -C₃ alkyl is for example naphthylmethyl, naphthylethyl,naphthylpropyl or naphthyl-1-methylethyl, especially naphthylmethyl. Thealkyl unit can be either in position 1 or in position 2 on the naphthylring system. Substituted naphthyl-C₁ -C₃ alkyl is substituted one tofour times, for example once, twice or three times, especially twice orthree times, on the aromatic rings.

C₁ -C₁₂ Alkoxy is a linear or branched radical and is, for example,methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy,isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy,2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxyor dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy,n-butyloxy, sec-butyloxy, isobutyloxy or tert-butyloxy, preferablymethoxy.

Halogen is fluorine, chlorine, bromine and iodine, especially fluorine,chlorine and bromine, preferably fluorine and chlorine. If C₁ -C₁₂ Alkylis substituted one or more times by halogen, then there are for example1 to 3 or 1 or 2 halogen substituents on the alkyl radical.

X as C₁ -C₂₀ alkylene is linear or branched alkylene, for examplemethylene, ethylene, propylene, 1-methylethylene 1,1-dimethylethylene,butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene,heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene,hexadecylene or octadecylene. In particular, X is C₁ -C₁₂ alkylene, forexample ethylene, decylene, ##STR12## X as C₂ -C₂₀ alkylene which isinterrupted one or more times by --O--, --S(O)_(p) -- or --NR₁₈ -- is,for example, interrupted 1-9 times, for example 1-7 times or once ortwice by --O--, --S(O)_(p) -- or --NR₁₈ --. This produces structuralunits such as, for example, --CH₂ --O--CH₂ --, --CH₂ --S--CH₂ --, --CH₂--N(CH₃)--CH₂ --, --CH₂ CH₂ --O--CH₂ CH₂ --, -- CH₂ CH₂ O!_(y) --,-- CH₂CH₂ O!_(y) --CH₂ --, where y=1-9, --(CH₂ CH₂ O)₇ CH₂ CH₂ --, --CH₂--CH(CH₃)--O--CH₂ --CH(CH₃)-- or --CH₂ --CH(CH₃)--O--CH₂ --CH₂ CH₂ --.--OR₆ -substituted C₁ -C₂₀ alkylene is, for example, ##STR13## C₃ -C₁₂Cycloalkylene is, for example, cyclopropylene, cyclopentylene,cyclohexylene, cyclooctylene, cyclododecylene, especially cyclopentyleneand cyclohexylene, preferably cyclohexylene. C₃ -C₁₂ Cycloalkylene isalso, however, for example, structural units such as ##STR14## in whichx and y independently of one another are 0-6 and the sum of x+y is ≦6,or ##STR15## in which x and y independently of one another are 0-7 andthe sum of x+y is ≦7.

C₂ -C₈ Alkenylene can be mono- or polyunsaturated and is, for example,ethenylene, 1-propenylene, 1-butenylene, 3-butenylene, 2-butenylene,1,3-pentadienylene, 5-hexenylene or 7-octenylene.

Examples of divalent aromatic hydrocarbon radicals are phenylene,stilbenylene, biphenylene, o-, m- and p-terphenylene,triphenylphenylene, naphthylene, binaphthylene, anthracenylene,phenanthrylene, pyrenylene, ferrocenylene, furanylene, thiophenylene,pyridinylene, quinolinylene or isoquinolinylene. ##STR16##

Substituted radicals phenylene, stilbenylene, biphenylene, o-, m- orp-terphenylene triphenylphenylene, naphthylene, binaphthylene,anthracylene, phenanthrylene, pyrenylene, ferrocenylene, furanylene,thiophenylene, pyridinylene, quinolinylene or isoquinolinylene aresubstituted one to four times, for example once, twice or three times,especially once or twice. Substituents on the 1,4-phenylene ring are inposition 2, 3, 5 or 6, especially in position 2 or 3 of the phenyl ring.Substituents on the 1,3-phenylene ring are in position 2, 4, 5 or 6,especially in position 4 or 5 of the phenyl ring.

Radicals suitable as a counterion Z⁺ to the negative borate in theformula I are those which are able to form positive ions.

Examples of these are alkali metals, especially lithium or sodium,quaternary ammonium compounds, dye cations or cationic transition metalcoordination complex compounds, especially ammonium ortetraalkylammonium.

Examples of tetraalkylammonium are, in particular, tetramethylammoniumand tetrabutylammonium, although trisalkylammonium ions, for exampletrimethylammonium, are also suitable. Suitable phosphonium and ammoniumcounterions are those of the formulae ⁺ PR_(w) R_(x) R_(y) R_(z) and ⁺NR_(w) R_(x) R_(y) R_(z), where R_(w), R_(x), R_(y), R_(z) independentlyof one another are hydrogen, unsubstituted or substituted alkyl,cycloalkyl, alkenyl, phenyl or arylalkyl. Substituents for these alkyl,cycloalkyl, alkenyl, phenyl or arylalkyl radicals are, for example,halide, hydroxyl, heterocycloalkyl (e.g. epoxy, aziridyl, oxetanyl,furanyl, pyrrolidinyl, pyrrolyl, thiophenyl, tetrahydrofuranyl, etc.),dialkylamino, amino, carboxyl, alkyl- and arylcarbonyl and aryloxy- andalkoxycarbonyl.

The tetravalent nitrogen may also be part of a 5- or 6-membered ring, inwhich case this ring may in turn be fused to other ring systems. Thesesystems may also contain additional heteroatoms, f or example S, N, O.

The tetravalent nitrogen may also be part of a polycyclic ring system,for example azoniapropellane. These systems m ay also contain furtherheteroatoms, for example S, N, O.

Also suitable are polyammonium salts and polyphosphonium salts,especially the bis salts, in which it is possible for the samesubstituents to be present as described above for the "mono" compounds.

The ammonium salts and phosphonium salts may also be substituted byneutral dyes (e.g. thioxanthenenes, thioxanthones, coumarins,ketocoumarins, etc.). Such salts are obtained by the reaction of theammonium salts and phosphonium salts, substituted by reactive groups(e.g. epoxy, amino, hydroxyl, etc.), with appropriate derivatives ofneutral dyes. Corresponding examples are described in EP-A 224 967QUANTACURE QTX ##STR17##

Similarly, ammonium salts and phosphonium salts can also be substitutedby colourless electron acceptors (e.g. benzophenones); examples of theseare QUANTACURE ABQ ##STR18## QUANTACURE BPQ ##STR19## and QUANTACURE BTC##STR20## from International Bio-Synthetics.

Other quaternary ammonium compounds which are of interest are, forexample, trimethylcetylammonium or cetylpyridinium compounds.

Other examples of ions to be used as positive counterions Z in thecompound of the formula I include the following: ##STR21## in which D isP, N or S and R is an alkyl or aryl radical. Also suitable are compoundssuch as ##STR22## (described by Yagci et al. in J. Polym. Sci. Part A:Polymer Chem. 1992, 30, 1987 and Polymer 1993, 34(6), 1130), orcompounds such as ##STR23## where R'=unsubstituted or substituted benzylor phenacyl (described in JP-A Hei 7 70221). In these compounds, thearomatic rings in the pyridinium may also be substituted.

Other positive counterions Z⁺ to the borate which can be employed areonium ions, for example iodonium or sulfonium ions.

Examples of such counterions to the borate are radicals of the formula##STR24## as described in EP-A 555 058 and EP-A 690 074. Also ofinterest as counterions are ##STR25## Further suitable counterions forthe novel borates are cations of the formula , ##STR26## in which R_(g)is an alkyl radical, especially ethyl, or is benzyl, and where thearomatic ring can carry further substituents. Other suitable counterionsare halonium ions, especially diaryliodonium ions, as described forexample in EP-A 334 056 and EP-A 562 897.

However, cations of ferrocenium salts are also suitable, as described inEP-A 94915 and EP A 109 851, for example ##STR27##

Other suitable onium cations, such as ammonium, phosphonium, sulfonium,iodonium, selonium, arsonium, tellonium and bismuthonium, are described,for example, in Japanese Patent Application Hei 6 266102.

Examples of cationic transition metal complex compounds which aresuitable as counterions are described in U.S. Pat. No. 4,954,414. Ofparticular advantage arebis(2,2'-bipyridine)(4,4'-dimethyl-2,2'-bipyridine)ruthenium,tris(4,4'-dimethyl-2,2'-bipyridine)ruthenium,tris(4,4'-dimethyl-2,2'-bipyridine)iron,tris(2,2',2"-terpyridine)ruthenium, tris(2,2'-bipyridine)ruthenium andbis(2,2'-bipyridine)(5-chloro-1,10-phenanthroline)ruthenium. Examples ofsuitable dyes are cations of triarylmethanes, for example malachitegreen, indolines, thiazines, for example methylene blue, xanthones,thioxanthones, oxazines, acridines, cyanines, rhodamines, phenazines,for example safranin, preferably cyanines and thioxanthones.

Some of the novel compounds exhibit good stability to acid and cantherefore also be employed in acidic formulations, and also for examplein combination with dyes containing acid groups.

The novel compounds of the formula I are prepared, for example, byaddition of from one to m+v equivalents of an organometallic reagentonto a corresponding borane (Ib): ##STR28## or (if u in formula I, asdefined above, is 0 and v is 1) ##STR29##

The definitions of the radicals are as given above.

It is also possible first to react the polyborane with an organometallicreagent MR₅ in which M is a metal atom, for example Li, Mg, etc., andthen in a second reaction step to replace the metal cation in theformula Ib by a different cation Z⁺ (e.g. tetraalkylammonium): ##STR30##

The reaction conditions for working with organometallic reagents aregenerally familiar to the skilled worker. Thus the reaction isexpediently carried out in an inert organic solvent, for example anether or aliphatic hydrocarbon, such as diethyl ether, tetrahydrofuranor hexane. Suitable organometallic reagents for preparing the novelpolyborates are, for example, the lithium compounds of the correspondingaliphatic and aromatic hydrocarbon radicals. It is also possible, forexample, to use Grignard reagents, zinc or sodium. The reaction with theorganometallic reagent is expediently carried out with the exclusion ofair in an inert gas atmosphere, for example under nitrogen. The reactionis generally performed with cooling to 0° C. or below followed byheating to room temperature. It is expedient to stir the reactionmixture. The products are isolated and purified by methods likewisegenerally known to the skilled worker, for example chromatography,recrystallization, etc. Thus, for example, impurities are expedientlyremoved by washing the product with a boiling solvent, followed byfiltration. It is also possible to obtain the polyborates directly fromsolution during the preparation of the polyborane precursors, withoutthe isolation thereof beforehand.

Where the novel compounds of the formula I contain a dye radical ascation, they are prepared by the cation exchange reaction of anappropriate borate salt with a dye. Examples of the borate saltssuitable for the exchange are the sodium, lithium, magnesium, ammoniumor tetraalkylammonium salts. The novel polyboranes (Ia) are obtained,for example, by the addition of a borane reagent of the formula ArBL₂ orAr₂ BL, in which Ar is an aryl radical and L is a leaving group, onto apolymetalated compound. The latter is generally prepared byhalogen←→metal exchange of a polyhalogenated aromatic compound with anorganometallic reagent, for example butyllithium, or with a metal, forexample magnesium. Polyboration can also be carried out in steps, forexample by repeated sequences of monometalation/monoborylation.Polyboranes can, moreover, be converted, for example by reaction ofmetalated aryl compounds, generally aryllithium or arylmagnesiumderivatives, into polydihaloborylated or polydialkoxyborylated andpolydiaryloxyborylated aromatic compounds. The conditions for suchreactions are generally familiar to the skilled worker and are asdescribed above. However, the polyboration reactions are generallycarried out at lower temperatures, for example -78° C.

Dimesitylfluoroborane, for example, can be prepared by the method ofPelter et al.; Tetrahedron 1993, 49, 2965. It is also commerciallyavailable. Bis(chloromesityl)fluoroborane andbis(dichloromesityl)fluoroborane can be obtained analogously frombromochloromesitylene. Diphenylisopropoxyborane anddi-o-tolylisopropoxyborane can be synthesized, for example, by additionof two equivalents of an appropriate Grignard reagent ontotriisopropoxyborane (cf. Cole et al., Organometallics, 1992, 11, 652).The corresponding diarylbromoboranes can be prepared, for example, bythe method of Haubold et al., J. Organomet. Chem. 1986, 315, 1.Phenyldifluoroborane, for example, is obtained by reaction ofphenyidibromoborane with titanium tetrafluoride (cf. Nahm et al., J.Organomet. Chem. 1972, 35, 9). 1,4-bis(difluoroboryl)benzene and1,4-bis(dibromoboryl)benzene can also be prepared by the methoddescribed by Nielsen et al. in J. Amer. Chem. Soc. 1957, 79, 3081. Thearyl halides required are either commercially available or can beprepared by methods known to the skilled worker and conventional in theart.

Boranes with chlorinated aromatic radicals, for example, can also beobtained by chlorination of the borane, for example: ##STR31## where Mesis mesityl, NCS is N-chlorosuccinimide, p-TsOH is p-toluenesulfonic acidand n is 1 or 2. Other chlorinating agents, for example chlorine gas,can also be employed.

Preferred compounds of the formula I are those in which n and o are both0.

Other advantageous compounds of the formula I are those in which m is 1.

Attention is merited by the compounds of the formula I in which R₁,R_(2a), R₃ und R₄ are identical.

Particular preference is given to those compounds of the formula I inwhich R₁, R_(2a), R₂, R₃, R₄, R₁₄ and R₁₅ independently of one anotherare 2-, 2,6- or 2,4,6-substituted phenyl or are naphthyl or anthracyl.

Advantageous compounds of the formula I are those in which R₁, R_(2a),R₂, R₃, R₄, R₁₄ and R₁₅ are C₁ -C₆ alkyl-, halo-, OR₆ - ortrifluoromethyl-substituted phenyl, 1-naphthyl or 1- or 9-anthracyl.

Also advantageous are compounds of the formula I in which R₁ is1-naphthyl, 2-(C₁ -C₆ alkyl)naphth-1-yl, 1-anthracyl, 9-anthracyl orferrocenyl.

Preference is given, moreover, to the compounds of the formula I inwhich X is C₁ -C₁₈ -alkylene which is unsubstituted or substituted byOR₆, NR₈ R₉, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ or halogen, or in which X is C₁-C₂₀ alkylene which is interrupted by one or more groups --O--, or inwhich X is phenylene, biphenylene, o-, m- or p-terphenylene,naphthylene, phenanthrylene or ferrocenylene, where the radicalsphenylene, biphenylene, o-, m- or p-terphenylene, naphthylene,phenanthrylene or ferrocenylene are unsubstituted or substituted by C₁-C₆ alkyl, OR₆, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃,BR₁₄ R₁₅ or halogen, or in which X is a radical of the formula II inwhich Y is --(CH₂)_(r) --, --C(O)--, --N--, --O--, --S(O)_(p) --, --CR₁₉R₂₀ --, ##STR32##

Other preferred compounds of the formula I are those in which

n and o are both 0,

m is the number 1,

R₁, R_(2a), R₂, R₃ and R₄ are phenyl substituted by C₁ -C₆ alkyl and/orhalogen, especially chlorine,

R₅ is C₁ -C₁₂ alkyl, (C₁ -C₄ alkyl)₃ Si-CH₂ - or phenyl,

X is unsubstituted phenylene, halo-substituted, especiallyfluoro-substituted, phenylene, biphenylene, o- or p-terphenylene,naphthylene, phenanthrylene, ferrocenylene or a radical of the formulaII in which

Y is --C(O)-- or ##STR33## s is 2, and Z is tetraalkylammonium, acyanine-dye cation or a thioxanthon cation.

In the prior art, borates have been used to date in combination withcoinitiator compounds or electron acceptor compounds, respectively, forexample dyes or transition metal complexes, as photoinitiators. It hasnow surprisingly been found that the combinations of polyboranes withcoinitiators or electron donor compounds, for example borates, also havegood photoinitiator properties.

The invention therefore additionally provides a photoinitiatorcomprising A) at least one borane of the formula VI ##STR34## in whichn' is a number from 0 to 50;

R₁ ', R₂ ', R₃ ' and R₄ ' are phenyl or another aromatic hydrocarbon,which radicals are unsubstituted or are substituted by unsubstituted orhalo-, OR₆ '- and/or NR₈ 'R₉ '-substituted C₁ -C₆ alkyl, OR₆ ', S(O)_(P)R₇ ', OS(O)₂ R₇ ', NR₈ 'R₉ ', C(O)NR₈ 'R₉ ', C(O)R₁₀ ', SiR₁₁ 'R₁₂ 'R₁₃', BR₁₄ 'R₁₅ ', halogen and/or P(O)_(q') R₁₆ 'R₁₇ ', at least one of theradicals R₁ ', R₂ ', R₃ ', and R₄ ' being a phenyl radical which issubstituted ortho to the bond to the boron atom or being anotheraromatic hydrocarbon radical which is sterically hindered ortho to theboron atom;

p' is a number from 0 to 2;

R₆ ' and R₇ ' independently of one another are unsubstituted orCOOR_(7a), OH, C₁ -C₁₂ alkoxy, CN or halo-substituted C₁ -C₁₂ alkyl,phenyl or phenyl-C₁ -C₆ alkyl, where the radicals phenyl or phenyl-C₁-C₆ alkyl are unsubstituted or substituted one to five times by C₁ -C₆alkyl, C₁ -C₁₂ alkoxy or halogen;

R_(7a) is C₁ -C₁₂ alkyl;

R₈ ', R₉ ', R₁₀ ', R₁₁ ', R₁₂ ', R₁₃ ', R₁₄ ' and R₁₅ ' independently ofone another are as defined for R₆ ' or are C₃ -C₁₂ cycloalkyl, or R₈ 'and R₉ ', together with the N atom to which they are attached, form a 5-or 6-membered ring which may additionally contain O or S atoms, or R₁₄ 'and R₁₅ ', together with the B atom to which they are attached, form a5- or 6-membered ring;

R₁₆ ' and R₁₇ ' independently of one another are as defined for R₁₀ ';

q' is 0 or 1; and

X' is C₁ -C₂₀ alkylene which is unsubstituted or substituted by OR₆ ',S(O)_(p') R₇ ', OS(O)₂ R₇ ', NR₈ 'R₉ ', C(O)OR₆ ', C(O)NR₈ 'R₉ ',C(O)R₁₀ ', SiR₁₁ 'R₁₂ 'R₁₃ ', BR₁₄ 'R₁₅ ', halogen or P(O)_(q') R₁₆ 'R₁₇', or X' is C₁ -C₂₀ alkylene which is interrupted by one or more groups--O--, --S(O)_(p') -- or --NR₁₈ '--, or X' is C₃ -C₁₂ cycloalkylene orC₂ -C₈ alkenylene, which radicals are unsubstituted or substituted byOR₆ ', S(O)_(p') R₇ ', OS(O)₂ R₇ ', NR₈ 'R₉ ', C(O)OR₆ ', C(O)NR₈ 'R₉ ',C(O)R₁₀ ', SiR₁₁ 'R₁₂ 'R₁₃ ', BR₁₄ 'R₁₅ ', halogen or P(O)_(q') R₁₆ 'R₁₇', or are interrupted by one or more groups --O--, --S(O)_(p') -- or--NR₁₈ '--,

or X' is a divalent aromatic hydrocarbon radical which is unsubstitutedor substituted by C₁ -C₆ alkyl, OR₆ ', S(O)_(p') R₇ ', OS(O)₂ R₇ ', NR₈'R₉ ', C(O)OR₆ ', C(O)NR₈ 'R₉ ', C(O)R₁₀ ', SiR₁₁ 'R₁₂ 'R₁₃ ', BR₁₄ 'R₁₅', halogen or P(O)_(q') R₁₆ 'R₁₇ ',

or X' is a radical of the formula VII or VIII ##STR35## in which Y' is--(CH₂)_(r') --, --C(O)--, --NR₁₈ ', --O--, --S(O)_(p') --, --CR₁₉ 'R₂₀'--, ##STR36## r' is 1, 2 or 3; s' is 2 or 3;

R₁₈ ' is as defined for R₆ ' or is hydrogen;

R₁₉ ' and R₂₀ ' are C₁ -C₆ alkyl or phenyl, or R₁₉ ' and R₂₀ ', togetherwith the C atom to which they are attached, form a 5- or 6-memberedring;

A' and Q' independently of one another are a direct bond, --(CH₂)_(r')--, --CH═CH-- --C(O)--, --NR₁₈ '-- or --S(O)_(p') --, --CR₁₉ 'R₂₀ '--,##STR37## or the radicals R₁ ', R₂ ', R₃ ', R₄ ' or X' form bridges toproduce radicals of the formula (IX) or (X) ##STR38## in which G' is--(CH₂)_(t') --, --CHCH--, --C(O)--, --NR₁₈ '--, --O-- or --S(O)_(p')--, --CR₁₉ 'R₂₀ '--, ##STR39## and t' is 0, 1 or 2,;

the radicals of the formulae (VII), (VIII), (IX) and (X) beingunsubstituted or substituted on the aromatic rings by OR₆ ', S(O)_(p')R₇ ', OS(O)₂ R₇ ', NR₈ 'R₉ ', C(O)OR₆ ', C(O)NR₈ 'R₉ ', C(O)R₁₀ ', SiR₁₁'R₁₂ 'R₁₃ ', BR₁₄ 'R₁₅ ' or halogen and it being possible for furtherphenyl rings to be fused to the phenyl rings of the formulae (VII),(VIII), (IX) and (X); and B) at least one electron donor compound.

The invention additionally provides photoinitiators comprising ascomponent B) at least one compound of the formula I and/or at least onecompound of the formula XI ##STR40## in which R_(a), R_(b), R_(c) andR_(d) independently of one another are C₁ -C₁₂ alkyl,trimethylsilylmethyl, phenyl, another aromatic hydrocarbon, C₁ -C₆alkylphenyl, allyl, phenyl-C₁ -C₆ alkyl, C₂ -C₈ alkenyl, C₂ -C₈ alkynyl,C₃ -C₁₂ cycloalkyl or saturated or unsaturated heterocyclic radicals,wherein the radicals phenyl, another aromatic hydrocarbon, phenyl-C₁ -C₆alkyl and saturated or unsaturated heterocyclic radical ar unsubstitutedor substituted by unsubstituted or halo-, OR₆ - and/or NR₈ R₉-substituted C₁ -C₆ alkyl, OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆,C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅, P(O)_(q) R₁₆ R₁₇ orhalogen;

p is 0, 1 or 2;

q is 0 or 1;

R₆ and R₇ are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- orhalo-substituted C₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substituted phenyl, or unsubstitutedor mono- to penta-C₁ -C₆ alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substitutedphenyl-C₁ -C₆ alkyl;

R_(7a) is C₁ -C₁₂ alkyl;

R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ independently of one another areas defined for R₆ or are C₃ -C₁₂ cycloalkyl, or R₈ and R₉, together withthe N atom to which they are attached, form a 5- or 6-membered ringwhich may additionally contain O or S atoms, or R₁₄ and R₁₅, togetherwith the B atom to which they are attached, form a 5- or 6-memberedring;

R₁₆ and R₁₇ independently of one another are as defined for R₆ or are C₃-C₁₂ cycloalkyl; and

E is a radical which is able to form positive ions, especially alkalimetals, ammonium, tetraalkylammonium, phosphonium- or sulphoniumradical.

The definitions of aromatic hydrocarbons, C₁ -C₁₂ alkyl, C₃ -C₁₂cycloalkyl, C₂ -C₈ alkenyl and phenyl-C₁ -C₆ alkyl, R₆ -R₁₇ are as givenabove. C₁ -C₆ Alkylphenyl is phenyl which is substituted one to fourtimes, for example one to three times, especially once, by C₁ -C₆alkyl-substituted phenyl. C₁ -C₆ Alkyl can have the same definitions asdescribed above for C₁ -C₁₂ alkyl up to the corresponding number of Catoms. C₂ -C₈ Alkynyl is, in particular, ethynyl. E as a radical whichforms positive ions has one of the definitions described above for Z.

Coinitiators used in accordance with the present invention are eitherelectron acceptor compounds (in combination with novel borates of theformula I) or electron donor compounds (in combination with polyboranesof the formula VI). Thus in this context the term coinitiator refers,for example, to sensitizers, such as thioxanthones, to reactionaccelerators, such as amines, thiols, etc., or to dyes. Examples ofsuitable electron donor compounds are borates, for example those of theformulae I and XI, such as triphenyl butyl borate, thiols, amines, forexample triethanolamine, N-phenylglycine or(2,5-dimethyl)-1-thia-3,4-diazole, organotin compounds, for examplebenzyltrimethylstannane, phosphines, arsines, for exampletriphenylphosphine or triphenylarsine, as described for example in JP-AHei 6 263809, sulfinates, for example sodium p-toluenesulfinate, orcarboxylates, for example ascorbic acid. Coinitiators of this kind aredescribed, for example, in Chemistry & Technology of UV & EB Formulationfor Coatings, Inks & Paints, Vol.3, page 344-348 (London, 1991).

It is of course also possible to add further coinitiaors or electronacceptor compounds, for example dyes, to the photoinitiators describedabove. The invention therefore additionally provides a photoinitiatorwhich in addition to components A) and B) comprises at least onecoinitiator or electron acceptor compound (C).

As already mentioned, the novel polyborate compounds of the formula Ican be employed per se as photoinitiators. However, it is also possibleto use them in combination with coinitiators or electron acceptorcompounds as photoinitiators. The invention therefore additionallyprovides a photoinitiator comprising at least one compound of theformula I according to claim 1 and at least one coinititator or electronacceptor compound. Examples of suitable electron acceptor compounds aretransition metal complex compounds or dyes. Suitable transition metalcomplex compounds, for example, are described in U.S. Pat. No.4,954,414, examples beingbis(2,2'-bipyridine)(4,4'-dimethyl-2,2'-bipyridine)-ruthenium,tris(4,4'-dimethyl-2,2'-bipyridine)ruthenium,tris(4,4'-dimethyl-2,2'-bipyridine)iron, tris(2,2',2"-terpyridine)ruthenium, tris(2,2'-bipyridine)ruthenium andbis(2,2'-bipyridin)-(5-chloro-1,10-phenanthroline)ruthenium. Suitabledyes which can be added as coinitiators (electron acceptor compounds)are described, for example, in U.S. Pat. No. 5,151,520. They are, by wayof example, triarylmethanes, such as malachite green, indolines,thiazines, such as methylene blue, xanthones, thioxanthones, oxazines,acridines or phenazines, such as safranin. Particularly suitable dyesare malachite green, methylene blue, safranin O, rhodamines of theformula ##STR41## in which R is alkyl or aryl and R' is hydrogen, alkylor aryl, for example rhodamine B, rhodamine 6G or violamine R, and alsosulforhodamine B or sulforhodamine G.

Other suitable dyes are fluorones, as described for example by Neckerset al. in J. Polym. Sci., Part A, Poly. Chem, 1995, 33, 1691-1703.##STR42## is of particular interest.

Examples of further suitable dyes are cyanines of the formula ##STR43##in which R=alkyl; n=0,1,2,3 or 4 and Y₁ =CH═CH, N--CH₃, C(CH₃)₂, O, S,Se. Preferred cyanines are those in which Y₁ in the above formula isC(CH₃)₂ or S.

The following dye compounds are also suitable as coinitiators: ##STR44##in which D is P, N or S and R is an alkyl or aryl radical. Preferredcompounds of the above formula are those in which DR₃ is N(CH₃)₃, N(C₂H₅)₃ or P(C₆ H₅)₃. Also suitable are compounds such as, for example,##STR45## as described for example by Yagci et al. in J. Polym. Sci.Part A: Polymer Chem. 1992, 30, 1987 and Polymer 1993, 34(6), 1130, orsuch as, for example, ##STR46## where R'=unsubstituted or substitutedbenzyl or phenacyl, described in JP-A Hei 7 70221. The abovementionedpyridinium compounds may also be substituted in the aromatic pyridiniumring.

Other suitable dyes can be found, for example, in U.S. Pat. No.4,902,604. These are azulene dyes. Of particular advantage ascoinitiators for the novel compounds are the compounds 1-18 listed incolumns 10 and 11 of this patent, in the Table. Examples of furthersuitable dyes are merocyanine dyes, as described in U.S. Pat. No.4,950,581 from column 6, line 20 to column 9, line 57.

As coinitiators for the novel compounds and photoinitiators it is alsopossible to use coumarin compounds. Examples of these are given in U.S.Pat. No. 4,950,581 in column 11, line 20 to column 12, line 42.

Other suitable coinitiators are xanthones or thioxanthones as described,for example, in U.S. Pat. No. 4,950,581, column 12, line 44 to column13, line 15.

Anionic dye compounds can also be employed as coinitiators and electronacceptor compounds. For instance, Rose Bengal, eosine or fluorescein arealso suitable. Other suitable dyes, for example from the triarylmethaneclass or azo class can be found in U.S. Pat. No. 5,143,818. Examples areEthyl Orange (Chem. Abstr. Reg. No. 62758-12-7), Brilliant Blue G (Chem.Abstr. Reg. No.6104-58-1), Brilliant Blue R (Chem. Abstr. Reg.No.6104-59-2), Lissamine Green B (Chem. Abstr. Reg. No. 3087-16-9) orPatent Blue VF (Chem. Abstr. Reg. No.129-17-9).

In accordance with the invention, the compounds of the formula I can beused as photoinitiators for the photopolymerization of ethylenicallyunsaturated compounds and mixtures containing such compounds. This usemay also be implemented in combination with another photoinitiatorand/or with other additives.

The invention therefore relates in addition to photopolymerizablecompositions comprising

(a) at least one ethylenically unsaturated photopolymerizable compoundand

(b) at least one compound of the formula I, it being possible for thecomposition to comprise, in addition to components (a) and (b), otherphotoinitiators and/or other additives.

Furthermore, the invention provides a composition comprising in additionto components (a) and (b) at least one compound of the formula XI##STR47## in which R_(a), R_(b), R_(c) and R_(d) independently of oneanother are C₁ -C₁₂ alkyl, trimethylsilylmethyl, phenyl, anotheraromatic hydrocarbon, C₁ -C₆ alkylphenyl, allyl, phenyl-C₁ -C₆ alkyl, C₂-C₈ alkenyl, C₂ -C₈ alkynyl, C₃ -C₁₂ cycloalkyl or saturated orunsaturated heterocyclic radicals, wherein the radicals phenyl, anotheraromatic hydrocarbon, phenyl-C₁ -C₆ alkyl and saturated or unsaturatedheterocyclic radical ar unsubstituted or substituted by unsubstituted orhalo-, OR₆ - and/or NR₈ R₉ -substituted C₁ -C₆ alkyl, OR₆, S(O)_(p) R₇,OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen;

p is 0, 1 or 2;

q is 0 or 1;

R₆ and R₇ are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- orhalo-substituted C₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substituted phenyl, or unsubstitutedor mono- to penta-C₁ -C₆ alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substitutedphenyl-C₁ -C₆ alkyl;

R_(7a) is C₁ -C₁₂ alkyl;

R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ independently of one another areas defined for R₆ or are C₃ -C₁₂ cycloalkyl, or R₈ and R₉, together withthe N atom to which they are attached, form a 5- or 6-membered ringwhich may additionally contain O or S atoms, or R₁₄ and R₁₅, togetherwith the B atom to which they are attached, form a 5- or 6-memberedring;

R₁₆ and R₁₇ independently of one another are as defined for R₆ or are C₃-C₁₂ cycloalkyl; and

E is a radical which is able to form positive ions, especially an alkalimetal, ammonium, tetraalkylammoinium, sulfonium- or phosphonium radical.

As already mentioned, it is advantageous to combine the novel boratecompounds with coinitiators, for example inter alia sensitizers (=energytransfer compounds). In this context, additionally and particularly,combinations with two or more different coinitiators or sensitizers, forexample mixtures of the novel borate compounds with onium salts andthioxanthones or coumarins or dyes, are highly effective. Preferredonium salts in these mixtures are diphenyliodonium hexafluorophosphate,(p-octyloxyphenyl)(phenyl)iodonium hexafluorophosphate, or correspondingother anions of these compounds, for example the halides; and alsosulfonium salts, for example triarylsulfonium salts (Cyracure® UVI 6990,Cyracure® UVI-6974 from Union Carbide; Degacure® KI 85 from Degussa orSP-150 und SP-170 from Asahi Denka). Preference is given, for example,to a mixture of the novel borate compounds with diphenyliodoniumhexafluorophosphate and isopropylthioxanthone, to a mixture of the novelborate compounds with (p-octyloxyphenyl)(phenyl)iodoniumhexafluorophosphate and isopropylthioxanthone, and to a mixture of thenovel borate compounds with ##STR48## (=Cyracure® UVI-6974) andisopropylthioxanthone. However, it is particularly advantageous to addyet another photoinitiator, of the α-amino ketone type, to theabovementioned mixtures. For example, mixtures of the novel borates withonium salts and thioxanthones or dyes and a-amino ketones are highlyeffective. A preferred example is the mixture of the novel boratecompounds with diphenyliodonium hexafluorophosphate or(p-octyloxyphenyl)(phenyl)iodonium hexafluorophosphate,isopropylthioxanthone and(4-methylthiobenzoyl)methyl-1-morpholino-ethane.

The invention therefore also provides a composition comprising inaddition to components (a) and (b) at least one neutral, anionic orcationic dye or a thioxanthone compound and an onium compound. Theabovementioned onium compounds are preferred.

The invention additionally provides a composition comprising in additionto components (a) and (b) at least one neutral, anionic or cationic dyeand an onium compound and a free-radical photoinitiator, especially ana-amino ketone compound.

The unsaturated compounds may include one or more olefinic double bonds.They may be of low (monomeric) or high (oligomeric) molecular mass.Examples of monomers containing a double bond are alkyl or hydroxyalkylacrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyland 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate andethyl methacrylate. Silicone acrylates are also advantageous. Otherexamples are acrylonitrile, acrylamide, methacrylamide, N-substituted(meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers suchas isobutyl vinyl ether, styrene, alkyl- and halostyrenes,N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.

Examples of monomers containing two or more double bonds are thediacrylates of ethylene glycol, propylene glycol, neopentyl glycol,hexamethylene glycol and of bisphenol A, and4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate or tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanurate or tris(2-acryloylethyl) isocyanurate.

Examples of polyunsaturated compounds of relatively high molecular mass(oligomers) are acrylisized epoxy resins, acrylisized polyesters,polyesters containing vinyl ether or epoxy groups, and alsopolyurethanes and polyethers. Further examples of unsaturated oligomersare unsaturated polyester resins, which are usually prepared from maleicacid, phthalic acid and one or more diols and have molecular weights offrom about 500 to 3000. In addition it is also possible to employ vinylether monomers and oligomers, and also maleate-terminated oligomers withpolyester, polyurethane, polyether, polyvinyl ether and epoxide mainchains. Of particular suitability are combinations of oligomers whichcarry vinyl ether groups and of polymers as described in WO 90/01512.However, copolymers of vinyl ether and maleic acid-functionalizedmonomers are also suitable. Unsaturated oligomers of this kind can alsobe referred to as prepolymers.

Particularly suitable examples are esters of ethylenically unsaturatedcarboxylic acids and polyols or polyepoxides, and polymers havingethylenically unsaturated groups in the chain or in side groups, forexample unsaturated polyesters, polyamides and polyurethanes andcopolymers thereof, alkyd resins, polybutadiene and butadienecopolymers, polyisoprene and isoprene copolymers, polymers andcopolymers containing (meth)acrylic groups in side chains, and alsomixtures of one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fattyacids such as linolenic acid or oleic acid. Acrylic and methacrylic acidare preferred.

Suitable polyols are aromatic and, in particular, aliphatic andcycloaliphatic polyols. Examples of aromatic polyols are hydroquinone,4,4'-dihydroxybiphenyl, 2,2-di(4-hydroxyphenyl)propane, and alsonovolaks and resols. Examples of polyepoxides are those based on theabovementioned polyols, especially the aromatic polyols, andepichlorohydrin. Other suitable polyols are polymers and copolymerscontaining hydroxyl groups in the polymer chain or in side groups,examples being polyvinyl alcohol and copolymers thereof orpolyhydroxyalkyl methacrylates or copolymers thereof. Further suitablepolyols are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol,octanediol, dodecanediol, diethylene glycol, triethylene glycol,polyethylene glycols having molecular weights of preferably from 200 to1500,1 ,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may be partially or completely esterified with one or withdifferent unsaturated carboxylic acids, and in partial esters the freehydroxyl groups may be modified, for example etherified or esterifiedwith other carboxylic acids.

Examples of esters are: trimethylolpropane triacrylate,trimethylolethane triacrylate, trimethylolpropane trimethacrylate,trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate,triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol diacrylate, dipentaerythritoltriacrylate, dipentaerythritol tetraacrylate, dipentaerythritolpentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritoloctaacrylate, pentaerythritol dimethacrylate, pentaerythritoltrimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritoltetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritoldiitaconate, dipentaerythritol trisitaconate, dipentaerythritolpentaitaconate, dipentaerythritol hexaitaconate, ethylene glycoldiacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate,1,4-butanediol diitaconate, sorbitol triacrylate, sorbitoltetraacrylate, pentaerythritol-modified triacrylate, sorbitoltetra-methacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,oligoester acrylates and methacrylates, glycerol diacrylate andtriacrylate, 1,4-cyclohexane diacrylate, bisacrylates andbismethacrylates of polyethylene glycol with a molecular weight of from200 to 1500, or mixtures thereof.

Also suitable as component (a) are the amides of identical or different,unsaturated carboxylic acids with aromatic, cycloaliphatic and aliphaticpolyamines having preferably 2 to 6, especially 2 to 4, amino groups.Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phaenylenediamine, bisphenylenediamine, di-β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- ordi(β-aminopropoxy)ethane. Other suitable polyamines are polymers andcopolymers, preferably with additional amino groups in the side chain,and oligoamides having amino end groups. Examples of such unsaturatedamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide,diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane,β-methacrylamidoethyl methacrylate and N-(β-hydroxyethoxy)ethyl!acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and from diols or diamines. Some of the maleic acid canbe replaced by other dicarboxylic acids. They can be used together withethylenically unsaturated comonomers, for example styrene. Thepolyesters and polyamides may also be derived from dicarboxylic acidsand from ethylenically unsaturated diols or diamines, especially fromthose with relatively long chains of, for example 6 to 20 C atoms.Examples of polyurethanes are those composed of saturated or unsaturateddiisocyanates and of unsaturated or, respectively, saturated diols.

Polybutadiene and polyisoprene, and copolymers thereof, are known.Examples of suitable comonomers are olefins, such as ethylene, propene,butene and hexene, (meth)acrylates, acrylonitrile, styrene or vinylchloride. Polymers with (meth)acrylate groups in the side chain arelikewise known. They may, for example, be reaction products of epoxyresins based on novolaks with (meth)acrylic acid, or may be homo- orcopolymers of vinyl alcohol or hydroxyalkyl derivatives thereof whichare esterified with (meth)acrylic acid, or may be homo- and copolymersof (meth)acrylates which are esterified with hydroxyalkyl(meth)acrylates.

The photopolymerizable compounds can be used alone or in any desiredmixtures. It is preferred to use mixtures of polyol (meth)acrylates.

Binders can also be added to the novel compositions, and this isparticularly expedient when the photopolymerizable compounds are liquidor viscous substances. The quantity of binder may, for example, be5-95%, preferably 10-90% and especially 40-90%, by weight relative tothe overall solids content. The choice of binder is made depending onthe field of application and on properties required for this field, suchas the capacity for development in aqueous and organic solvent systems,adhesion to substrates and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight ofabout 5000 to 2000000, preferably 10000 to 1000000. Examples are: homo-and copolymers of acrylates and methacrylates, for example copolymers ofmethyl methacrylate/ethyl acrylate/methacrylic acid, poly(alkylmethacrylates), poly(alkyl acrylates); cellulose esters and celluloseethers, such as cellulose acetate, cellulose acetobutyrate,methylcellulose, ethylcellulose; polyvinylbutyral, polyvinylformal,cyclized rubber, polyethers such as polyethylene oxide, polypropyleneoxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane,chlorinated polyolefins, polyvinyl chloride, vinyl chloride/vinylidenechloride copolymers, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene-vinyl acetate), polymers such as polycaprolactam andpoly(hexamethyleneadipamide), and polyesters such as poly(ethyleneglycol terephthalate) and poly(hexamethylene glycol succinate).

The unsaturated compounds can also be used as a mixture withnon-photopolymerizable, film-forming components. These may, for example,be physically drying polymers or solutions thereof in organic solvents,for instance nitrocellulose or cellulose acetobutyrate. They may also,however, be chemically and/or thermally curable (heat-curable) resins,examples being polyisocyanates, polyepoxides and melamine resins. Theuse of heat-curable resins at the same time is important for use insystems known as hybrid systems, which are photopolymerized in a firststage and then crosslinked by means of thermal aftertreatment in asecond stage. The invention additionally provides compositions which inaddition to components (a) and (b) comprise at least one electronacceptor (c), for example a dye or a UV absorber. Suitable dyes (c) aredescribed above. Other suitable examples are benzoxanthene,benzothioxanthene, pyronine or porphyrin dyes. Examples of UV absorberswhich are suitable as electron acceptor (c) are thioxanthonederivatives, coumarins, benzophenone, benzophenone derivatives orderivatives of hexaarylbisimidazole (HABI). Examples of suitablehexaarylbisimidazole derivatives are described in U.S. Pat. Nos.3,784,557, 4,252,887, 4,311,783, 4,459,349, 4,410,621 and 4,622,286. Ofparticular advantage are 2-o-chlorophenyl-substituted derivatives, suchas 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-bisimidazole.Other UV absorbers suitable in this context are, for example, polycyclicaromatic hydrocarbons, for example anthracene or pyrene, and thetriazines described in EP-A-137 452, in DE-A-27 18 254 and in DE-A-22 43621. Further suitable triazines can be found in U.S. Pat. No. 4,950,581,column 14, line 60 to column 18, line 44. Of particular advantage aretrihalomethyltriazines, for example2,4-bis(trichloromethyl)-6-(4-styrylphenyl)-s-triazine. Other suitableelectron acceptors (c) are benzopteridinediones (described in JP Hei 02113002), substituted benzophenones (e.g. Michler's ketone, QUANTACUREABQ, QUANTACURE BPQ and QUANTACURE BTC from InternationalBiosynthetics), trichloromethyltriazine (described in JP Hei 01 033548),metal complexes (described in JP Hei 04 261405), porphyrins (describedin JP Hei 06 202548 and JP Hei 06 195014), coumarins and ketocoumarins(described in U.S. Pat No. 4,950,581 and JP Hei 06 175557),p-aminophenyl compounds (described in EP-A 475153), xanthenes (describedin JP Hei 06 175566) or pyrylium, thiopyrylium and selenopyrylium dyes(described in JP Hei 06 175563).

As already mentioned above, it is also possible to provide the novelpolyborates of the formula I with dye cations, sulphonium- or iodoniumcations and to employ them thus as photoinitiator. The inventiontherefore provides, furthermore, a composition comprising

(a) at least one ethylenically unsaturated photopolymerizable compoundand

(b) at least one polyborate anion of the formula Ia ##STR49## in whichthe radicals R₁, R₂, R_(2a), R₃, R₄, R₅ and X, and also n, m, o, u andv, are as defined in claim 1, and

(c) a dye cation, sulfonium- or iodonium cation.

Also provided by the invention is a composition as described abovecomprising, in addition, at least one further borate compound of theformula XI ##STR50## in which R_(a), R_(b), R_(c) and R_(d)independently of one another are C₁ -C₁₂ alkyl, trimethylsilylmethyl,phenyl, another aromatic hydrocarbon, C₁ -C₆ alkylphenyl, allyl,phenyl-C₁ -C₆ alkyl, C₂ -C₈ alkenyl, C₂ -C₈ alkynyl, C₃ -C₁₂ cycloalkylor saturated or unsaturated heterocyclic radicals, wherein the radicalsphenyl, another aromatic hydrocarbon, phenyl-C₁ -C₆ alkyl and saturatedor unsaturated heterocyclic radical ar unsubstituted or substituted byunsubstituted or halo-, OR₆ - and/or NR₈ R₉ -substituted C₁ -C₆ alkyl,OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁R₁₂ R₁₃, BR₁₄ R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen;

p is 0, 1 or 2;

q is 0 or 1;

R₆ and R₇ are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- orhalo-substituted C₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substituted phenyl, or unsubstitutedor mono- to penta-C₁ -C₆ alkyl-, -C₁ -C₁₂ alkoxy- or -halo-substitutedphenyl-C₁ -C₆ alkyl;

R_(7a) is C₁ -C₁₂ alkyl;

R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ independently of one another areas defined for R₆ or are C₃ -C₁₂ cycloalkyl, or R₈ and R₉, together withthe N atom to which they are attached, form a 5- or 6-membered ringwhich may additionally contain O or S atoms, or R₁₄ and R₁₅, togetherwith the B atom to which they are attached, form a 5- or 6-memberedring;

R₁₆ and R₁₇ independently of one another are as defined for R₆ or are C₃-C₁₂ cycloalkyl; and

E is a radical which is able to form positive ions, especially an alkalimetal, ammonium, tetraalkylammoinium, sulfonium- or phosphonium radical.

Likewise provided by the invention is a composition comprising (a) atleast one ethylenically unsaturated photopolymerizable compound and (b)at least one photoinitiator as described above comprising A) at leastone borane of the formula VI and B) at least one electron donorcompound. As a further component this composition may comprise anelectron aceptor compound.

The novel composition may in addition to the photoinitiator comprisingA) and B) also comprise further photoinitiators and/or additives.Specific examples of such photoinitiators are given later on.

The invention provides, moreover, a composition comprising at least oneborate of the formula I and at least one dye which changes or loses itscolour during or after irradiation, which dye may also, as a cation, bepart of the compound of the formula I. Examples of such dyes are cyaninedyes and pyrylium dyes.

In addition to the photoinitiator the photopolymerizable mixtures mayinclude various additives. Examples of these are thermal inhibitors,which are intended to prevent premature polymerization, examples beinghydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol orsterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol. Inorder to increase the stability on storage in the dark it is possible,for example, to use copper compounds, such as copper naphthenate,stearate or octoate, phosphorus compounds, for exampletriphenylphosphine, tributylphosphine, triethyl phosphite, triphenylphosphite or tribenzyl phosphite, quaternary ammonium compounds, such astetramethylammonium chloride or trimethylbenzylammonium chloride, orhydroxylamine derivatives, for example N-diethylhydroxylamine. Toexclude atmospheric oxygen during the polymerization it is possible toadd paraffin or similar waxlike substances which, being of inadequatesolubility in the polymer, migrate to the surface at the beginning ofpolymerization and form a transparent surface layer which prevents theingress of air. It is also possible to apply an oxygen-impermeablelayer. Light stabilizers which can be added in a small quantity are UVabsorbers, for example those of the hydroxyphenylbenzotriazole,hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type.These compounds can be used individually or in mixtures, with or withoutsterically hindered amines (HALS). Examples of such UV absorbers andlight stabilizers are

1. 2-(2'-hydroxyphenyl)benzotriazoles for example2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-di-tertamyl-2'-hydroxyphenyl)benzotriazole,2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,mixture of2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-5'-2-(2-ethyl-hexyloxy)carbonylethyl!-2'-hydroxyphenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3'-tert-butyl-5'-2-(2-ethylhexyloxy)carbonylethyl!-2'-hydroxyphenyl)benzotriazole,2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, and2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol!;transesterification product of 2- 340-tert-butyl-5'-(2-methoxy-carbonylethyl)-2'-hydroxyphenyl!benzotriazolewith polyethylene glycol 300; R -CH₂ CH₂ --COO(CH₂)₃ !₂ - whereR=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.

2. 2-Hydroxybenzophenones, for example the 4-hydroxy-, 4-methoxy-,4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tertbutylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

4. Acrylates, for example isooctyl or ethyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, butyl or methylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

5. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(2,2,6,6-tetramethylpiperidyl) succinate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation productof 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetraoate,1,1'-(1,2-ethandiyl)bis(3,3,5,5-tetramethyl-piperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis-(1,2,2,6,6-pentamethylpiperidyl)2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro 4.5!decane-2,4-dione,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, condensationproduct ofN,N'-bis-(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane, condensation product of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro4,5!decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione and3-dodecyl-1-(1,2,2,6,6-penta-methyl-4-piperidyl)-pyrrolidine-2,5-dione.

6. Oxalamides, for example 4,4'-dioctyloxyoxanilide,2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide,2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of o- andp-methoxy- and of o- and p-ethoxy-disubstituted oxanalides.

7. 2-(2-Hydroxyohenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxy-phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-4-dodecyl/tridecyl-oxy-(2-hydroxypropyl)oxy-2-hydroxyphenyl!-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

8. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythrityl diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrityl diphosphite, bis-isodecyloxy pentaerythrityldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythrityldiphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythrityldiphosphite, tristearyl sorbityl triphosphite,tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzod,g!-1,3,2-dioxaphosphocine,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzod,g!-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl) ethylphosphite.

To accelerate the photopolymerization it is possible to add amines, forexample triethanolamine, N-methyldiethanolamine, p-dimethylaminobenzoateor Michler's ketone. The action of the amines can be intensified by theaddition of aromatic ketones of the benzophenone type. Examples ofamines which can be used as oxygen scavengers are substitutedN,N-dialkylanilines, as are described in EP-A-339 841. Otheraccelerators, coinitiators and autoxidizers are, for example, thiols,thioethers, disulfides and phosphines, as described, for example, inEP-A-438 123 and GB-A-2 180 358.

The curing process can be assisted, in particular, by compositions whichare pigmented (for example with titanium dioxide), and also by adding acomponent which under thermal conditions forms free radicals, forexample an azo compound such as2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for instance a hydroperoxideor peroxycarbonate, for example t-butyl hydroperoxide, as described forexample in EP-A-245 639.

Further customary additives, depending on the intended use, arefluorescent whiteners, fillers, pigments, dyes, wetting agents andlevelling assistants. In order to cure thick and pigmented coatings itis appropriate to add glass microspheres or pulverized glass fibres, asdescribed for example in U.S. Pat. No. 5,013,768.

The invention also provides compositions comprising as component (a) atleast one ethylenically unsaturated photopolymerizable compound which isemulsified or dissolved in water.

Many variants of such radiation-curable aqueous prepolymer dispersionsare commercially available. A prepolymer dispersion is understood asbeing a dispersion of water and at least one prepolymer dispersedtherein. The concentration of water in these systems is, for example,from 5 to 80% by weight, in particular from 30 to 60% by weight. Theconcentration of the radiation-curable prepolymer or prepolymer mixtureis, for example, from 95 to 20% by weight, in particular from 70 to 40%by weight. In these compositions the sum of the percentages given forwater and prepolymer is in each case 100, with auxiliaries and additivesbeing added in varying quantities depending on the intended use.

The radiation-curable, film-forming prepolymers which are dispersed inwater and are often also dissolved are mono- or polyfunctional,ethylenically unsaturated prepolymers which are known per se for aqueousprepolymer dispersions, can be initiated by free radicals and have acontent of, for example, from 0.01 to 1.0 mol of polymerizable doublebonds per 100 g of prepolymer and an average molecular weight of, forexample, at least 400, in particular from 500 to 10 000. Prepolymerswith higher molecular weights, however, may also be considered dependingon the intended application. Use is made, for example, of polyesterscontaining polymerizable C--C double bonds and having an acid number ofnot more than 10, of polyethers containing polymerizable C--C doublebonds, of hydroxyl-containing reaction products of a polyepoxide,containing at least two epoxide groups per molecule, with at least oneα,β-ethylenically unsaturated carboxylic acid, of polyurethane(meth)acrylates and of acrylic copolymers which containα,β-ethylenically unsaturated acrylic radicals, as are described inEP-A-12 339. Mixtures of these prepolymers can likewise be used. Alsosuitable are the polymerizable prepolymers described in EP-A-33 896,which are thioether adducts of polymerizable prepolymers having anaverage molecular weight of at least 600, a carboxyl group content offrom 0.2 to 15% and a content of from 0.01 to 0.8 mol of polymerizableC--C double bonds per 100 g of prepolymer. Other suitable aqueousdispersions, based on specific alkyl (meth)acrylate polymers, aredescribed in EP-A-41 125, and suitable water-dispersible,radiation-curable prepolymers of urethane acrylates can be found inDE-A-29 36 039. Further additives which may be included in theseradiation-curable aqueous prepolymer dispersions are dispersionauxiliaries, emulsifiers, antioxidants, light stabilizers, dyes,pigments, fillers, for example talc, gypsum, silicic acid, rutile,carbon black, zinc oxide, iron oxides, reaction accelerators, levellingagents, lubricants, wetting agents, thickeners, matting agents,antifoams and other auxiliaries customary in paint technology. Suitabledispersion auxiliaries are water-soluble organic compounds which are ofhigh molecular mass and contain polar groups, examples being polyvinylalcohols, polyvinylpyrrolidone and cellulose ethers. Emulsifiers whichcan be used are nonionic emulsifiers and, if desired, ionic emulsifiersas well.

The quantity of photoinitiator (b) in the photopolymerizablecompositions is expediently from 0.05 to 15% by weight, preferably from0.1 to 5% by weight, based on the composition.

In certain cases it may be of advantage to use mixtures of two or moreof the novel photoinitiators. As already mentioned above, it is ofcourse also possible to use mixtures with other known photoinitiators,for example mixtures with benzophenone, benzophenone derivatives,acetophenone, acetophenone derivatives, for example cc-hydroxycycloalkylphenyl ketones, dialkoxyacetophenones, α-hydroxy- orα-aminoacetophenones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers andbenzil ketals, monoacyl phosphine oxides, bisacylphosphine oxides,titanocenes or ferrocenes. Examples of particularly suitablephotoinitiators are: 1-(4-dodecylbenzoyl)-1-hydroxy-1 -methylethane,1-(4-isopropylbenzoyl)-1-hydroxy-1-methylethane,1-benzoyl-1-hydroxy-1-methylethane, 1-4-(2-hydroxyethoxy)benzoyl!-1-hydroxy-1-methylethane, 1-4-(acryloyloxyethoxy)benzoyl!-1-hydroxy-1-methylethane, diphenyl ketone,phenyl 1-hydroxy-cyclohexyl ketone,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,1-(3,4-di-methoxyphenyl)-2-benzyl-2-dimethylamino-butan-1-one,(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane, benzil dimethylketal, bis(cyclopentadienyl)bis(2,6-difluoro-3-pyrrylphenyl)titanium,cyclopentadienyl-arene-iron(II) complex salts, for example (η⁶-iso-propylbenzene)(η⁵ -cyclopentadienyl)iron(II) hexafluorophosphate,trimethylbenzoyidiphenylphosphine oxide ,bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide orbis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide. Other suitableadditional photoinitiators can be found in U.S. Pat. No. 4,950,581column 20, line 35 to column 21, line 35. Also suitable are triazinecompounds, for example the triazines described in EP-A-137 452, inDE-A-27 18 254 and in DE-A-22 43 621. Further suitable triazines can befound in U.S. Pat. No. 4,950,581, column 14, line 60 to column 18, line44. There is particular interest in trihalomethyltriazines, for example2,4-bis(trichloromethyl)-6-(4-styrylphenyl)-s-triazine. Where the novelphotoinitiators are employed in hybrid systems, use is made, in additionto the novel free-radical hardeners, of cationic photoinitiators, forexample peroxide compounds, such as benzoyl peroxide (other suitableperoxides are described in U.S. Pat. No. 4,950,581 column 19, lines17-25), aromatic sulfonium, phosphonium or iodonium salts (as describedfor example in U.S. Pat. No. 4,950,581, column 18, line 60 to column 19,line 10) or cyclopentadienyl-arene-iron(II) complex salts, for example(η⁶ -isopropylbenzene)-(η⁵ -cyclopentadien-yl)iron(II)hexafluorophosphate.

The invention therefore further provides compositions which in additionto the photoinitiator (b) also comprise at least one furtherphotoinitiator (d) and/or other additives.

Compositions comprising as additional photoinitiator (d) a titanocene, aferrocene, a benzophenone, a benzoin alkyl ether, a benzil ketal, a4-aroyl-1,3-dioxolane, a dialkoxyacetophenone, an α-hydroxy- orα-aminoacetophenone, an α-hydroxycycloalkyl phenyl ketone, a xanthone, athioxanthone, an anthraquinone or a mono- or bisacylphosphine oxide, ormixtures thereof, as additional photoinitiator are of particularinterest.

Also of interest are compositions in which a further additive used is areadily reducible compound, especially a halogenated hydrocarbon.Suitable readily reducible compounds are, for example, halogenatedhydrocarbons such as, in particular, ##STR51##

The term readily reducible compound is to be understood in this contextas including compounds as described in U.S. Pat. No. 4,950, 581,examples including iodonium salts, sulfonium salts, organic peroxides,compounds having carbon-halide bonds (trichloromethyltriazines),heterocyclic sulfur compounds, and other photoinitiators (α-aminoketones). Examples of other additives are heterocycles as described inthe Patents and Patent Applications U.S. Pat. No. 5,168,032, JP 02244050, JP 02 054268, JP 01 017048 and DE 383308. Examples of furtheradditives are aromatic imines, described in U.S. Pat. No. 5,079,126, andaromatic diazo compounds described in U.S. Pat. No. 5,200,292 (e.g.iminoquinone diazides), thiols, described in U.S. Pat. No. 4,937,159 andthiols ,and N,N-dialkylanilines, described in U.S. Pat. No. 4,874,685.It is also possible to employ two or more of the stated coinitiators orelectron acceptors and additives in combination.

The photopolymerizable compositions can be used for various purposes,for example as printing ink, as a clear finish, as a white finish, forexample for wood or metal, as a coating material, inter alia for paper,wood, metal or plastic, as a powder coating, as a daylight-curablecoating for roadmarking and the marking of buildings, for photographicreproduction techniques, for holographic recording materials, for imagerecording techniques or for producing printing plates which can bedeveloped with organic solvents or with aqueous alkalis, for producingmasks for screen printing, as dental filling compositions, as adhesives,including pressure-sensitive adhesives, as laminating resins, as etchresists or permanent resists, and as solder masks for electroniccircuits, for producing three-dimensional articles by mass curing (UVcuring in transparent moulds) or by the stereolithography technique, asis described, for example, in U.S. Pat. No. 4,575,330, for producingcomposite materials (for example styrenic polyesters, which may ifdesired contain glass fibres and/or other fibres and other auxiliaries)and other thick-layered compositions, for coating or sealing electroniccomponents, or as coatings for optical fibres.

The novel compounds may additionally be employed as initiators foremulsion, bead or suspension polymerizations, as polymerizationinitiators for fixing ordered states of liquid-crystalline monomers andoligomers, or as initiators for fixing dyes on organic materials.

In coating materials, use is frequently made of mixtures of a prepolymerwith polyunsaturated monomers, which may additionally include amonounsaturated monomer as well. It is the prepolymer here whichprimarily dictates the properties of the coating film, and by varying itthe skilled worker is able to influence the properties of the curedfilm. The polyunsaturated monomer functions as a crosslinking agentwhich renders the film insoluble. The monounsaturated monomer functionsas a reactive diluent, which is used to reduce the viscosity without theneed to employ a solvent.

Unsaturated polyester resins are usually used in two-component(two-pack) systems together with a monounsaturated monomer, preferablywith styrene. For photoresists, specific one-component Systems are oftenused, for example polymaleimides, polychalcones or polyimicles, asdescribed in DE-A-23 08 830.

The novel compounds and mixtures thereof can also be used asfree-radical photoinitiators or photoinitiating systems forradiation-curable powder coatings. The powder coatings can be based onsolid resins and monomers containing reactive double bonds, for examplemaleates, vinyl ethers, aceryates, acrylamides and mixtures thereof. Afree-radically UV-curable powder coating can be formulated by mixingunsaturated polyester resins with solid acrylamides (for example methylmethylacrylamidoglycolate) and a novel free-radical photoinitiator, suchformulations being as described, for example, in the paper "RadiationCuring of Powder Coatino", Conference Proceedings, Radtech Europe 1993by M. Wittig and Th. Gohmann. Free-radically UV-curable powder coatingscan also be formulated by mixing unsaturated polyester resins with solidacrylates, methacrylates or vinyl ethers and with a novel photoinitiator(or photoinitiator mixture). The powder coatings may also comprisebinders as are described, for example, in DE-A-42 28 514 and in EP-A-636669.

The UV-curable powder coatings may additionally comprise white orcoloured pigments. For example, preferably rutiletitanium dioxide can beemployed in concentrations of up to 50% by weight in order to give acured powder coating of good hiding power. The procedure normallycomprises electrostatic or tribostatic spraying of the powder onto thesubstrate, for example metal or wood, melting of the powder by heating,and, after a smooth film has formed, radiation-curing of the coatingwith ultraviolet and/or visible light, using for example medium-pressuremercury lamps, metal halide lamps or xenon lamps. A particular advantageof the radiation-curable powder coatings over their heat-curablecounterparts is that the flow time after melting of the powder particlescan be delayed if desired in order to ensure the formation of a smooth,high-gloss coating. In contrast to heat-curable systems,radiation-curable powder coatings can be formulated to melt at lowertemperatures without the unwanted effect of shortening their lifetime.For this reason, they are also suitable as coatings for heat-sensitivesubstrates, for example wood or plastics. In addition to the novelphotoinitiators, the powder coating formulations may also include UVabsorbers. Appropriate examples are listed above in sections 1-8.

The novel photocurable compositions are suitable, for example, ascoating materials for substrates of all kinds, for example wood,textiles, paper, ceramic, glass, plastics such as polyesters,polyethylene torephthalate, polyolefins or cellulose acetate, especiallyin the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg orCo and GaAs, Si or SiO₂ to which it is intended to apply a protectivelayer or, by means of imagewise exposure, to generate a reproducedimage.

Coating of the substrates can be carried out by applying to thesubstrate a liquid composition, a solution or a suspension. The choiceof solvents and the concentration depend principally on the type ofcomposition and on the coating technique. The solvent should be inert,i.e. it should not undergo a chemical reaction with the components andshould be able to be removed again, after coating, in the course ofdrying. Examples of suitable solvents are ketones, ethers and esters,such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone,cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran,2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol,1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl3-ethoxypropionate. The solution is applied uniformly to a substrate bymeans of known coating techniques, for example by spin coating, dipcoating, knife coating, curtain coating, brushing, spraying, especiallyby electrostatic spraying, and reverse-roll coating, and also by meansof electrophoretic deposition. It is also possible to apply thephotosensitive layer to a temporary, flexible support and then to coatthe final substrate, for example a copper-clad circuit board, bytransferring the layer via lamination.

The quantity applied (coat thickness) and the nature of the substrate(layer support) are dependent on the desired field of application. Therange of coat thicknesses generally comprises values from about 0.1 μmto more than 100 μm.

The novel radiation-sensitive compositions find application as negativeresists, having a very high sensitivity to light and being able to bedeveloped in an aqueous alkaline medium without swelling. They aresuitable as photoresists for electronics (electroplating resist, etchresist, solder resist), the production of printing plates, such asoffset, flexographic and relief printing plates or screen printingand/or the production of dies, for use in chemical milling or as amicroresist in the production of integrated circuits. The possible layersupports, and the processing conditions of the coated substrates, arejust as varied.

The compounds according to the invention also find application for theproduction of one- or more-layered materials for the image recording oreimage reproduction (copies, reprography), which may be uni- orpolychromatic. Furthermore the materials are suitable for colourproofing systems. In this technology formulations containingmicrocapsules can be applied and for the image production the radiationcuring can be followed by a thermal treatment. Such systems andtechnologies and their applications are for example disclosed in U.S.Pat. No. 5,376,459.

Substrates used for photographic information recording include, forexample, films of polyester, cellulose acetate or polymer-coated papers;substrates for offset printing formes are specially treated aluminum,substrates for producing printed circuits are copper-clad laminates, andsubstrates for producing integrated circuits are silicon wafers. Thelayer thicknesses for photographic materials and offset printing formsare generally from about 0.5 μm to 10 μm, while for printed circuitsthey are from 1.0 μm to about 100 μm.

Following the coating of the substrates, the solvent is removed,generally by drying, to leave a coat of the photoresist on thesubstrate. The term "imagewise" exposure includes both exposure througha photomask comprising a predetermined pattern, for example a slide,exposure by means of a laser beam, which for example is moved undercomputer control over the surface of the coated substrate and in thisway produces an image, and irradiation with computer-controlled electronbeams.

Following the imagewise exposure of the material and prior todevelopment, it may be advantageous to carry out thermal treatment for ashort time. In this case only the exposed sections are thermally cured.The temperatures employed are generally 50°-1500° C., preferably 8°-130°C.; the period of thermal treatment is in general between 0.25 and 10minutes.

The photocurable composition may additionally be used in a process forproducing printing plates or photoresists as is described, for example,in DE-A-40 13 358. In such a process the composition is exposed for ashort time to visible light with a wavelength of at least 400 nm,without a mask, prior to, simultaneously with or following imagewiseirradiation.

After the exposure and, if implemented, thermal treatment, the unexposedareas of the photosensitive coating are removed with a developer in amanner known per se.

As already mentioned, the novel compositions can be developed by aqueousalkalis. Particularly suitable aqueous-alkaline developer solutions areaqueous solutions of tetraalkylammonium hydroxides or of alkali metalsilicates, phosphates, hydroxides and carbonates. Minor quantities ofwetting agents and/or organic solvents may also be added, if desired, tothese solutions. Examples of typical organic solvents, which may beadded to the developer liquids in small quantities, are cyclohexanone,2-ethoxyethanol, toluene, acetone and mixtures of such solvents.

Photocuring is of great importance for printing inks, since the dryingtime of the binder is a critical factor for the production rate ofgraphic products, and should be in the order of fractions of seconds.UV-curable inks are particularly important for screen printing.

As already mentioned above, the novel mixtures are also highly suitablefor producing printing plates. This application uses, for example,mixtures of soluble linear polyamides or styrene/butadiene and/orstyrene/isoprene rubber, polyacrylates or polymethyl methacrylatescontaining carboxyl groups, polyvinyl alcohols or urethane acrylateswith photopolymerizable monomers, for example acrylamides and/ormethacrylamides, or acrylates and/or methacrylates, and aphotoinitiator. Films and plates of these systems (wet or dry) areexposed over the negative (or positive) of the printed original, and theuncured parts are subsequently washed out using an appropriate solvent.

Another field where photocuring is employed is the coating of metals, inthe case, for example, of the coating o metal plates and tubes, cans orbottle caps, and photocuring of polymer coatings, for example of flooror wall coverings based on PVC.

Examples of the photocuring of paper coatings are the colorlessvarnishing of labels, record sleeves and book covers.

Also of interest is the use of the novel compounds for curing shapedarticles made from composite compositions. The composite compositionconsists of a self-supporting matrix material, for example a glass fibrefabric, or alternatively, for example, plant fibres cf. K.-P. Mieck, T.Reussmann in Kunststoffe 85 (1995), 366-370!, which is impregnated withthe photocuring formulation. Shaped parts comprising compositecompositions, when produced using the novel compounds, attain a highlevel of mechanical stability and resistance. The novel compounds canalso be employed as photocuring agents in moulding, impregnating andcoating composition s as are described, for example, in EP-A-7086.Examples of such compositions are gel coat resins, which are subject tostringent requirements regarding curing activity and yellowingresistance, and fibre-reinforced mouldings, such as, for example, lightdiffusing panels which are planar or have lengthwise or crosswisecorrugation. Techniques for producing such mouldings, such as handlay-up, spray lay-up, centrifugal casting or filament winding, aredescribed, for example, by P. H. Selden in "GlasfaserverstarkteKunststoffe", page 610, Springer Verlag Berlin-Heidelberg-New York 1967.Examples of articles which can be produced by these techniques areboats, fibre board or chipboard panels with a double-sided coating ofglass fibre-reinforced plastic, pipes, containers, etc. Further examplesof moulding, impregnating and coating compositions are UP resin gelcoats for mouldings containing glass fibres (GRP), such as corrugatedsheets and paper laminates. Paper laminates may be based on urea resinsor melamine resins. Prior to production of the laminate, the gel coat isproduced on a support (for example a film). The novel photocurablecompositions can also be used for casting resins or for embeddingarticles, for example electronic components, etc. They can additionallybe employed for lining cavities and pipes. Curing is carried out usingmedium-pressure mercury lamps as are conventional in UV curing. However,there is also particular interest in less intense lamps, for example ofthe type TL 40W/03 or TL40W/05. The intensity of these lamps correspondsapproximately to that of sunlight. It is also possible to use directsunlight for curing. A further advantage is that the compositecomposition can be removed from the light source in a partly cured,plastic state and can be shaped, with full curing taking placesubsequently.

The compositions and compounds according to the invention can be usedfor the production of waveguide and optical switches wherein advantageis taken of the development of a difference in the index of refractionbetween irradiated and unirradiated areas.

The use of photocurable compositions for imaging techniques and for theoptical production of information carriers is also important. In suchapplications, as already described above, the layer (wet or dry) appliedto the support is irradiated through a photomask with UV or visiblelight, and the unexposed areas of the layer are removed by treatmentwith a solvent (=developer). Application of the photocurable layer tometal can also be carried out by electrodeposition. The exposed areasare polymeric through crosslinking and are therefore insoluble andremain on the support. Appropriate colouration produces visible images.Where the support is a metallized layer, the metal can, followingexposure and development, be etched away at the unexposed areas orreinforced by electroplating. In this way it is possible to produceprinted electronic circuits and photoresists.

The photosensitivity of the novel compositions extends in general fromabout 200 nm through the UV region into the infrared region (about 20000 nm, in particular 1200 nm) and therefore spans a very broad range.Suitable radiation is present, for example, in sunlight or light fromartificial light sources. Consequently, a large number of very differenttypes of light source are employed. Both point sources and arrays ("lampcarpets") are suitable. Examples are carbon arc lamps, xenon arc lamps,medium-, high- and low-pressure mercury lamps, possibly doped with metalhalide (metal-halogen lamps), microwave-excited metal vapour lamps,excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argonincandescent lamps, electronic flashlamps, photographic floodlamps,electron beams and X-rays, produced by means of synchrotrons or laserplasma. The distance between the lamp and the substrate to be exposed inaccordance with the invention may vary depending on the intendedapplication and the type and output of the lamp, and may be, forexample, from 2 cm to 150 cm. Laser light sources, for example excimerlasers, are especially suitable. Lasers in the visible region or in theIR region can also be employed. In this case, the high sensitivity ofthe novel materials and the possibility of adapting the dye to the laserline are very advantageous. By this method it is possible to produceprinted circuits in the electronics industry, lithographic offsetprinting plates or relief printing plates, and also photographicimage-recording materials.

The invention additionally provides for the use of the above-describedcomposition for preparing pigmented and unpigmented paints andvarnishes, printing inks, powder coatings, printing plates, adhesives,dental compositions, waveguides, optical switches, colour proofingsystems, composite compositions, glass fibre cable coatings, screenprinting stencils, resist materials, for photographic reproductions, forencapsulating electrical and electronic components, for producingmagnetic recording materials, for producing three-dimensional objects bystereolithography, and as image recording material, especially forholographic recordings.

The invention additionally provides a coated substrate which is coatedon at least one surface with a composition as described above, anddescribes a process for the photographic production of relief images, inwhich a coated substrate is subjected to imagewise exposure and then theunexposed portions are removed with a solvent. Of particular advantagein this context is the laser beam exposure already mentioned above.

The invention also provides a process for the photopolymerization ofnonvolatile monomeric, oligomeric or polymeric compounds containing atleast one ethylenically unsaturated double bond, which comprises addingat least one compound of the formula I or a photoinitator as describedabove to said compounds and irradiating the resulting composition withlight having a wavelength ranging from 200 nm up to and including theinfrared region.

The novel borate compounds can be employed not only as initiators forphotopolymerization reactions but also as thermal polymerizationinitiators.

Consequently, the invention also provides for the use of the compoundsof formula I as initiators for the thermal polymerization of compoundscontaining ethylenically unsaturated double bonds, and a process for thethermal polymerization of compounds containing ethylenically unsaturateddouble bonds, which comprises employing at least one compound of theformula I as polymerization initiator.

The examples which follow illustrate the invention in more detail. Partsand percentages are, as in the remainder of the description and in theclaims, by weight, unless stated otherwise. Where alkyl radicals havingmore than three carbon atoms are referred to without any mention ofspecific isomers, the n-isomers are meant in each case.

I. Preparation of the Boranes ##STR52## EXAMPLE 11,4-Bis(dimesitylboryl)benzene

R₁ -R₄ =mesityl, n=1; X=1,4-phenylene

Method A

One equivalent of butyllithium (0.01 mol) in hexane is added over thecourse of 15 minutes at -78° C. to a solution of 2.36 g (0.01 mol) of1,4-dibromobenzene in 10 ml of diethyl ether. The temperature is slowlyraised to -50° C. over the course of one hour, and the mixture is thencooled again to -78° C. Subsequently, 2.68 g (0.01 mol) of soliddimesitylfluoroborane are added, and the mixture is allowed to warm upto room temperature and is stirred for an hour. The mixture is pouredinto 50 ml of water and filtered to give 3.1 g of a beige solid. Theproduct is purified by washing with boiling acetonitrile, giving 2.1 g(52% of theory) of 1-bromo-4-dimesitylborylbenzene. A solution of thisborane in 20 ml of tetrahydrofuran (THF) is cooled to -78° C. andtreated with 1 equivalent (0.05 mol) of butyllithium in hexane. The redsolution is allowed to warm up to -50° C. over the course of 30 minutesand is then cooled again to -78° C. Subsequently, 1.34 g (0.005 mol) ofsolid dimesitylfluoroborane are added, and the reaction mixture isallowed to warm up to room temperature and is stirred for an hour. Themixture Is poured into 50 ml of water and filtered to give a whitesolid. The product is purified by washing with boiling acetonitrile,giving 2.23 g (78% of theory) of the pure bisborane. Physical data aregiven in Table 1.

Method B

One equivalent (0.01 mol) of butyllithium in hexane is added over thecourse of 15 minutes at -78° C. to a solution of 2.36 g (0.01 mol) of1,4-dibromobenzene in 20 ml of THF. The suspension is allowed to warmslowly up to 50° C. over the course of 30 minutes, and is then cooledagain to -78° C. and treated with 2.68 g of (0.01 mol) of soliddimesitylfluoroborane. The reaction mixture is allowed to warm up toroom temperature and is stirred for half an hour. The mixture is cooledto -78° C. and treated as described above in Method A in succession withbutyllithiuim and dimesitylfluoroborane. After warming to roomtemperature, the mixture is poured into 100 ml of water and filtered andthe product is washed with boiling acetonitrile to give 4.88 g (85% oftheory) of the product.

Method C

2 equivalents of butyllithium (0.1 mol) in hexane are added at roomtemperature to a solution of 11.8 g (0.05 mol) of 1,4-dibromobenzene in200 ml of hexane. The mixture is refluxed for 3 hours. The suspensionwhich formed is cooled to -78° C. and treated with 26.8 g (0.1 mol) ofsolid dimesitylfluoroborane. After warming to room temperature, thereaction mixture is poured into 200 ml of water and subjected twice toextraction with 50 ml of hexane. The combined organic phases are driedover magnesium sulphate, filtered and concentrated, resulting in ayellow solid. Recrystallization from hexane gives 17.0 g (i.e. 59% oftheory) of 1,4-bis(dimesitylboryl)benzene.

Method D

2 equivalents (0.08 mol) of t-butyllithium in pentane are added over thecourse of one hour at 0° C. to a solution of 8 g (0.04 mol) ofbromomesitylene in 100 ml of hexane. The mixture is refluxed for 3hours. After cooling to 0° C., a solution of 4.17 g (0.01 mol) of1,4-bis(dibromoboryl)benzene in 80 ml of hexan is added to the mixtureand the batch is refluxed overnight. The thick suspension produced ispoured into 200 ml of water and subjected twice to extraction with 50 mlof hexane. The combined organic phases are dried over magnesiumsulphate, filtered and concentrated. A yellow solid is formed which isrecrystallized from hexane, giving 3.0 g (52% of theory) of1,4-bis(dimesitylboryl)benzene.

Method E

1,4-Bis(dimesitylboryl)benzene can also be obtained by the methoddescribed by A. Schultz and W. Kaim in Chem. Ber. 1989, 122, 1863-1868,by reacting one equivalent of 1,4-bis(bromomagnesio)benzene with 2equivalents of dimesitylfluoroborane under reflux in THF, in a yield of6% of theory.

EXAMPLE 2 1-Dimesitylboryl-4-diphenylborylbenzene

R₁,R₂ =mesityl; R₃,R₄ =phenyl; n=1; X=1,4-phenylene

The compound is prepared in accordance with Method B described above,using 1 equivalent of dimesitylfluoroborane and 1 equivalent ofdiphenylisopropoxyborane. The crude product is obtained by concentratingthe reaction mixture under a high vacuum and treating the solid residue,under argon, with hexane. Filtration, concentration of the filtrate andrecrystallization of the residue from acetonitrile give 3.0 g (61% oftheory) of the pale yellow title product, which is sensitive to air.Physical data are given in Tabelle 1.

EXAMPLE 3 1-Bis(chloromesityl)boryl-4-dimesitylborylbenzene

R₁,R₂ =mesityl; R₃,R₄ =chloromesityl; n=1; X=1,4-phenylene

The compound is prepared in accordance with Method B described above,using 1 equivalent of bis(chloromesityl)fluoroborane and 1 equivalent ofdimesitylfluoroborane. Physical data are given in Table 1.

EXAMPLE 4 1,4-Bis bis(chloromesityl)boryl!benzene

R₁ -R₄ =chloromesityl; n=1; X=1,4-phenylene

The compound is prepared by Method B described above using 2 equivalentsof bis(chloromesityl)fluoroborane. Physical data are given in Table 1.

EXAMPLE 5 1,3-Bis(dimesitylboryl)benzene

R₁ -R₄ =mesityl; n=1; X=1,3-phenylene

The compound is prepared by Method B described above and obtained in ayield of 83%. Physical data are given in Table 1.

EXAMPLE 5 1-Fluoro-3,5-bis(dimesitylboryl)benzene

R₁ -R₄ =mesityl; n=1; X=5-fluoro-1,3-phenylene

The compound is prepared by Method C described above in diethyl ether at-50° C. and obtained in a yield of 61%. Physical data are given in Table1.

EXAMPLE 7 1-Bis(chloromesityl)boryl-3-dimesitylborylbenzene

R₁,R₂ =mesityl; R₃,R₄ =chloromesityl; n=1; X=1,3-phenylene

The compound is prepared by Method B described above in a yield of 86%,using 1 equivalent of bis(chloromesityl)fluoroborane and 1 equivalent ofdimesitylfluoroborane. Physical data are given in Table 1.

EXAMPLE 8 4,4'-Bis(dimesitylboryl)biphenyl

R₁ -R₄ =mesityl; n=1; X=4,4'-biphenylene

The compound is obtained by Method C described above in diethyl ether at0° C. in a yield of 70%. Physical data are given in Table 1.

EXAMPLE 9 4-Bis(chloromesityl)boryl-4'-dimesitylborylbiphenyl

R₁, R₂ =mesityl; R₃,R₄ =chloromesityl; n=1; X=4,4'-biphenylene

The compound is obtained by Method B described above in a yield of 71%,using 1 equivalent of bis(chloromesityl)fluoroborane and 1 equivalent ofdimesitylfluoroborane. Physical data are given in Table 1.

EXAMPLE 10 4,4'-Bis(dimesitylboryl)benzophenone ethylene ketal

R₁ -R₄ =Mesityl; n=1; X= ##STR53##

The compound is prepared by Method C described above in diethyl ether at0° C. Physical data are given in Table 1.

EXAMPLE 11 4,4'-Bis(dimesitylboryl)benzophenone

R₁ -R₄ =mesityl; n=1; X= ##STR54##

The compound is obtained in a yield of 64% by hydrolysis of the compoundfrom Example 10 in a mixture of ethanol, water and concentratedhydrochloric acid. Physical data are given in Table 1.

EXAMPLE 12 4,4"-Bis(dimesitylboryl)-p-terphenyl

R₁ -R₄ =mesityl; n=1; X=4,4"-p-terphenylene

The compound is obtained in a yield of 73% by Method B described aboveusing the appropriate starting materials. Physical data are given inTable 1.

EXAMPLE 13 4,4"-Bis bis(chloromesityl)boryl!-p-terphenyl

R₁ -R₄ =chloromesityl, N=1; X=4,4"-p-terphenylene

The compound is obtained in a yield of 51% by Method B described above,using 2 equivalents of bis(chloromesityl)fluoroborane. Physical data aregiven in Table 1.

EXAMPLE 14 4,4"Bis(dimesitylboryl)-o-terphenyl

R₁ -R₄ =mesityl; n=1; X=4,4"-o-terphenylene

The compound is obtained in a yield of 43% by Method B described above,using the appropriate starting materials. Physical data are given inTable 1.

EXAMPLE 15 1,5-Bis(dimesitylboryl)naphthalene

R₁ -R₄ =mesityl; n=1; X=1,5-naphthylene

The compound is obtained in a yield of 86% by Method C described abovein diethyl ether at -78° C., using the appropriate starting materials.Physical Data are given in Table 1.

EXAMPLE 16 1,5-Bis bis(chloromesityl)boryl!naphthalene

R₁ -R₄ =chloromesityl; n=1; X=1,5-naphthylene

The compound is obtained in a yield of 83% by Method C described abovein diethyl ether at -78° C., using the appropriate starting materials.Physical data are given in Table 1.

EXAMPLE 17 1,7-Bis(dimesitylboryl)naphthalene

R₁ -R₄ =mesityl; n=1; X=1,7-naphthylene

The compound is obtained In a yield of 37% by Method C described abovein diethyl ether at -78° C., using the appropriate starting materials.Physical data are given in Table 1.

EXAMPLE 18 9-Dimesitylboryl-10-di(2-methylphenyl)borylanthracene

R₁,R₂ =mesityl; R₃,R₄ =o-tolyl; n=1; X=9,10-anthracylene

The compound is prepared by Method A described above by way of9-bromo-10-dimesitylborylanthracene. The bromium-lithium exchange andsubsequent treatment with ditolylbromoborane gives the desired productin a yield of 55%. Physical data are given in Table 1.

EXAMPLE 19 9,10-Bis(dimesitylboryl)anthracene

R₁ -R₄ =mesityl; n=1; X=9,10-anthracylene

The compound is obtained in a yield of 45% by Method C described abovein diethyl ether at 0° C., using the appropriate starting materials.Physical data are given in Table 1.

EXAMPLE 20 Polymesitylphenylborane ##STR55##

4 equivalents of tert-butyllithium (0.020 mol) in pentane are added overthe course of one hour at -78° C. to a solution of 1.86 g (0.005 mol) ofdiiodomesitylene in THF. The suspension is stirred at -78° C. for 3hours and then treated with 0.57 g (0.0045 mol) of phenyidifluoroborane.The reaction mixture is warmed to room temperature and stirred for 2hours. It is poured into 50 ml of water and the mixture is subjectedtwice to extraction with 50 ml of ethyl acetate. The combined organicphases are dried over magnesium sulphate, filtered and concentrated. Thecrude product is purified by washing with boiling acetonitrile, giving0.37 g (38% of theory) of a white solid. GPC (Gel PermeationChromatography) reveals M_(n) =1730; M_(w) =1061, M_(n) /M_(w) =1.63.Further physical data are given in Table 1.

EXAMPLE 21 1,1'-Bis(dimesitylboryl)ferrocene ##STR56##

The compound is obtained in a yield of 10% by Method D described above,using the appropriate starting materials.

EXAMPLE 22 1,4-Bis bis(dinitromesityl)boryl!benzene

R₁ -R₄ =dinitromesityl; n=1; X=1,4-phenylene

2.87 g (0.005 mol) of 1,4-bis(dimesitylboryl)benzene (=compound fromExample 1) are added in portions over the course of 25 minutes at -78°C. to a mixture of 13.9 ml (25.5 g, 0.26 mol) of concentrated sulfuricacid and 24.9 ml (37.8 g, 0.6 mol) of nitric acid. The mixture is warmedto -40° C. over the course of 30 minutes, and then water is addedcarefully until reaction is no longer exothermic. The precipitated solidis isolated by filtration, washed with water and dried.Recrystallization from ethyl acetate gives 0.55 g (0.0006 mol, i.e. 13%of theory) of a white solid. Physical data are given in Table 1.

EXAMPLE 23 1,7-Bis bis(chloromesityl)boryl!naphthyl

R₁ -R₄ =chloromesityl; n=1; X=1,7-naphthylene

The compound is prepared in analogy to Method B described above andobtained in a yield of 57%. Physical data are given in Table 1.

EXAMPLE 24 1,4-Bis bis(dichloromesityl)boryl!benzene

R₁ -R₄ =dichloromesityl; n=1; X=1,4-phenylene

The compound is prepared in analogy to Method B described above usingbis(dichloromesityl)fluoroborane and is obtained in a yield of 13%.Physical data are given in Table 1.

EXAMPLE 25 1,6- and 1,8-bis(dimesitylboryl)pyrene (mixture of the 1,6-and 1,8-compounds)

R₁ -R₄ =mesityl; n=1; X=1,6- und 1,8-pyrenyl

The mixture of compounds is prepared in analogy to Method C describedabove in THF at -78° C. and is obtained in a yield of 74%. Physical dataare given in Table 1.

EXAMPLE 26 1,6- and 1,8-Bis bis(chloromesityl)boryl!pyrene (mixture ofthe 1,6- and 1,8 compounds)

R₁ -R₄ =chloromesityl; n=1; X=1,6- und 1,8-pyrenyl

The mixture of compounds is prepared in analogy to Method C describedabove in THF at -78° C. and is obtained in a yield of 56%. Physical dataare given in Table 1.

EXAMPLE 27 Poly(4-butylphenyl)durylborane

R₁, R₃ =4-butylphenyl; R₂, R₄ =duryl; n=2-22, X=1,4-durene

The compound is prepared in analogy to the method described for compound20, using diiododurene and potassium p-tert-butylphenyltrifluoroborate,and is obtained in a yield of 33%. Physical data are given in Table 1.

EXAMPLE 28 ##STR57##

The compound is prepared by Method C described above using 4 equivalentsof t-butyllithium in THF at -78° C. and is obtained in a yield of 77%.Physical data are given in Table 1.

EXAMPLE 29 3,5-Bis(dimesitylboryl)-1-trimethylsilylbenzene

R₁ -R₄ =mesityl; n=1; X=1-trimethylsilyl-phen-3-yl-5-yl

a) 1-bromo-3,5-bis(dimesitylboryl)benzene

6.25 ml (0.01 mol) of 1.6M butyllithium in hexane are added over 5minutes at -78° C. to a suspension of 3.14 g (0.01 mol) of1,3,5-tribromobenzene in 50 ml of diethyl ether. The reaction mixture isstirred at -78° C. for 2 hours, during which a yellow-orange suspensionis produced. 2.68 g (0.01 mol) of solid dimesitylfluoroborane are added,and the reaction mixure is warmed to room temperature over about onehour. The mixture is then diluted with 50 ml of hexane and cooled to 0°C. The solid produced is filtered, washed several times with cold hexaneand then washed with water and, finally, with methanol, until the solidis colourless. Drying gives 3.54 g (0.0073 mol; i.e. 73% of theory) of awhite solid (1,3-dibromo-5-dimesitylborylbenzene). Followingpurification by chromatography (hexane; SiO₂) a melting point of190°-191° C. is obtained.

Elemental analysis for C₂₄ H₂₅ BBr₂ gives: C calc.: 59.55%; found:59.52% H calc.: 5.21%; found: 5,12%

To prepare 1-bromo-3,5-bis(dimesitylboryl)benzene,1,3-dibromo-5-dimesitylborylbenzene is again reacted by theabove-described method with butyllithium and dimesitylfluoroborane. Theyield of 1-bromo-3,5-bis(dimesitylboryl)benzene is 76% of theory (forphysical data see Example 32).

b) 3,5-bis(dimesitylboryl)-1-trimethylsilylbenzene

6.25 ml (0.01 mol) of a 1.6M solution of butyllithium in hexane areadded at -78° C. to a solution of 6.53 g of (0.01 mol) of1-bromo-3,5-bis(dimesitylboryl)benzene in 50 ml of THF. The mixture isstirred at -78° C. for 1.5 h, and then 2.0 ml (3.0 g; 0.015 mol) oftrimethylsilyl iodide are added over the course of 10 minutes. After themixture has been stirred again at -78° C. for one hour, it is allowed towarm up to room temperature and stirred for about 12 hours. It is thendiluted with water and subjected twice to extraction with 50 ml of ethylacetate each time. Drying over magnesium sulfate and concentration gives7.15 g of a viscous oil. Following purification by chromatography(hexane, SiO₂), 3.7 g (0.0058 mol, i.e. 58% of theory) of the titlecompound are obtained as a white solid. Physical data are given in Table1.

EXAMPLE 30 3,5-Bis(dimesitylboryl)-1-diisopropylaminocarbonyl-benzene

R₁ -R₄ =mesityl; n=1; X=1-diisopropylaminocarbonyl-phen-3-yl-5-yl

The compound is prepared in analogy to Method b) described in Example29, using Cl(CO)N(i-C₃ H₇)₂ as electrophile. Recrystallization fromhexane gives the product in a yield of 46%. Physical data are given inTable 1.

EXAMPLE 31 ##STR58##

The compound is prepared in analogy to Method b) described in Example29, using ##STR59## as electrophile. Purification by washing in boilinghexane gives a yield of 62%. Physical data are given in Table 1.

EXAMPLE 32 1-Bromo-3,5-bis(dimesitylboryl)benzene

R₁ -R₄ =mesityl; n=1; X=1-bromophen-3-yl-5-yl

The preparation of this borane is described in Example 29 stage a).Physical data are given in Table 1.

EXAMPLE 33 1-Bromo-3,5-bis bis(chloromesityl)boryl!benzene R₁ -R₄=chloromesityl; n=1; X=1-bromophen-3-yl-5-yl

This compound is prepared similarly to the compound described in Example32, using bis(chloromesityl)fluoroborane as electrophile. Physical dataare given in Table 1.

EXAMPLE 34 1,3,5-Tris bis(chloromesityl)boryl!benzene

R₁ -R₄ =chloromesityl; n=1; X=1-bis(chloromesityl)borylphen-3-yl-5-yl

The compound is prepared similarly to the compound from Example 29,using (dichloromesityl)fluoroborane as electrophile both in stage a) andin stage b). Physical data are given in Table 1.

EXAMPLE 35 Bis 3-(dimesitylboryl)-2,4,6-(trimethyl)phenyl!-phenylborane##STR60## a) (1-Bromo-2,4,6-trimethylphenyl)dimesitylborane

67 ml (0.1 mol) of a 1.5M solution of t-butyllithium in pentane areadded dropwise through a syringe over the course of 2.5 h and at -78° C.to a suspension of 13.9 g (0.05 mol) of dibromomesitylene in 100 ml THF.The mixture is stirred at -78° C. for 1.5 hours more and then soliddimesitylfluoroborane is added, and the reaction mixture is allowed towarm to room temperature over the course of 2 hours and then dilutedwith 200 ml of water. Extraction is subsequently carried out twice with50 ml of ethyl acetate each time. Drying over magnesium sulfate andconcentration give a beige-white solid. Washing with boilingacetonitrile gives 15.62 g (i.e. 70% of theory) of the desired borane.Elemental analysis for C₂₇ H₃₂ BBr gives: C calc.: 72.51%; C found,72.78%; H calc.: 7.21%; H found: 7.30%.

b) Title compound

A solution of 8.94 g (0.02 mol) of the compound from stage a) in 50 mlof THF is treated at -78° C. with 12.5 ml (0.02 mol) of a 1.6M solutionof butyllithium in hexane. After stirring at -78° C. for 1 hour, the redsolution is treated with 1.3 ml (1.39 g; 0.011 mol) ofphenyidifluoroborane and allowed to warm to room temperature over thecourse of one hour. The reaction mixture is diluted with 100 ml of waterand subjected to extraction with ethyl acetate. Drying over magnesiumsulfate and concentration give a white solid. Chromatography (hexane,SiO₂) gives 4.14 g (0.0112 mol, i.e. 56% of theory) of the desiredproduct. Physical data are given in Table 1.

EXAMPLE 36 1,4-Bis bis(chloromesityl)boryl!naphthalene

R₁ -R₄ =chloromesityl; n=1; X=1,4-naphthylene

The compound is obtained in a yield of 71% by Method B described aboveusing bis(chloromesityl)fluoroborane. Physical data are given in Table1.

EXAMPLE 37 1,4-Bis(dimesitylboryl)naphthalene

R₁ -R₄ =mesityl; n=1; X=1,4-naphthylene

The compound is obtained in a yield of 71% by Method B described above.Physical data are given in Table 1.

EXAMPLE 38 1,4,7-Tris(dimesitylboryl)naphthalene

R₁ -R₄ =mesityl; n=1; X=7-dimesitylboryinaphth-1-yl-4-yl

The compound is prepared by method B described above but with threesuccessive additions of butyllithium and dimesitylfluoroborane. It isobtained in a yield of 63%. Physical data are given in Table 1.

EXAMPLE 39 4,4'-Bis bis(chloromesityl)boryl!biphenyl

R₁ -R₄ =dichloromesityl; n=1; X=4,4'-biphenylene

The compound is obtained in a yield of 22% by Method B described aboveusing bis(chloromesityl)fluoroborane. The physical data are given inTable 1.

EXAMPLE 40 1,3,5-Tris(dimesitylboryl)benzene

R₁ -R₄ =mesityl; n=1; X=dimesitylborylphen-3-yl-5-yl

The compound of Example 40 is prepared similarly to the compound fromExample 29 by threefold treatment with dimesitylfluoroborane. The yieldis 73%. Physical data are given in Table 1.

                  TABLE 1                                                         ______________________________________                                        Boranes                                                                       Compd.                                                                        from  Melting                                                                 Ex.   point  °C.!                                                                     .sup.1 H-NMR in CDCl.sub.3 at 300 Hz δ ppm! J            ______________________________________                                                        Hz!                                                           1     253-255  7.43(s, 4); 6.79(8); 2.28(s, 12); 1.98(s, 24)                  2     *        7.63-7.18(m, 14); 6,83(s, 4); 2.30(s, 6); 2.05(s, 12)          3     232-233  7.45(d, 2, J=7.8); 7.39(d, 2, j=7.8); 6.89(s, 2); 6.80                        (s, 4); 2.37(s, 6); 2.29(s, 6); 2.06(s, 6); 1.97(s, 18)        4     248-250  7.40(s, 4); 6.90(s, 4); 2.37(s, 12); 2.06                                     (s, 12); 1.97(s, 12)                                           5     172-173  7.54(d, 2, J=7.4); 7.52(s, 1); 7.29(t, 1, J=7.4);                             6.78(s, 8); 2.27(s, 12); 1.94(s, 24)                           6     143-145  7.29(s, 1); 7.19(d, 2, J=9.1); 6.75(s, 8); 2.27(s, 12);                       1.94(s, 24)                                                    7     68-70    7.60(d, 1, J=7.4); 7.52(d, 1, J=7.4); 7.33(s, 1);                             7.31(t, 1, J=7.4);p 6.83(m, 2); 6.75(s, 4); 2.35(m,                           6); 2.26(s, 6); 2.05(s, 3); 2.02(s, 3); 1.96(s, 3);                           1.95(s, 12); 1.92(s, 3)                                        8     254-255  7.64(d, 4, J=8.1); 7.58(d, 4, J=8.1); 6.83(s, 8);                             2.31(s, 12); 2.03(s, 24)                                       9     228-232  7.67-7.53(m, 8); 6.93(s, 2); 6.83(s, 4); 2.39(s, 6);                          2.31(s, 6); 2.12(s, 6); 2.03(s, 12); 2.03(s, 6)                10    234-236  7.46(s, 8); 6.80(s, 8), 4.07(s, 4); 2.29(s, 12);                              1.96(s, 24)                                                    11    208-209  7.73(d, 4, J=7.8); 7.53(d, 4, J=7.8); 6.80(s, 8);                             2.30(s, 12); 2.00(s, 24)                                       12    >250     7.74(s, 4); 7.63(d, 4, J=8.2); 7.60(d, 4, J=8.2);                             6.84(s, 8); 2.32(s, 12); 2.04(s, 24)                           13    192-197  7.44(s, 4); 7.64(d, 4, J=8.2); 7.56(d, 4, J=8.2);                             6.93(s, 4); 2.40(s, 12); 2.13(s, 12); 2.03(s, 12)              14    210-220  7.40-7.41(m, 4); 7.30(d, 4, J=11.0); 7.08(d, 4,                               J=11.0); 6.80(s, 8); 2.30(s, 12); 1.97(s, 24)                  15    >250     7.95(d, 2, J=8.3); 7.42(d, 2, J=6.5); 7.15(dd, 2,                             J=8.3 und 6.5), 6,77(br s, 8) 2.29(s, 12);                                    1.93(br s, 24)                                                 16    >250     7.92(br d, 2, J=8.3); 7.41(br d, 2, J=6.6); 7.18(br dd,                       2, J=8.3 and 6.6); 6.89(br s, 2); 6.87(br s, 2);                              2.37(s, 12); 2.10(br s, 12; 1.94(br s, 12)                     17    248-250  8.00(s, 1); 7.88(m, 1); 7.75(d, 1, J=8.2);                                    7.49-7.41(m, 3); 6.74(s, 4); 6.62(br s, 4); 2.31(s, 6);                       2.25(s, 6); 1.80(s, 12); 1.76(br s, 12)                        18    247-250  8.06(m, 2); 7.67(m, 2); 7.41-7.25(m, 4);                                      7.18-7.10(m, 8); 6.86(br s, 2); 6.66(br s, 2); 2.27(s,                        6); 2.17(br s, 6); 2.08(s, 6); 1.67(br s, 6)                   19    259-260  7.97(m, 4); 7.02(m, 4); 6.74(br s, 8); 2.19(s, 12);                           2.08(br s, 12); 1.63(br s, 12)                                 20    184-185  7.51-7.24(m, 5); 6.80(m, 1); 2.00(br s, 6);                                   1.83(br s, 3)                                                  21    >250     6.75(s, 8); 4.74(br s, 4); 4.42(br s, 4); 2.28(s, 36)          22    >230     7.66(s, 4); 2.33(s, 12); 2.08(s, 24)                           23    224-227  7.94(d, 1, J=8); 7.90(br s, 1); 7,77(d, 1, J=8);                              7.55-7.40(m, 3); 6.87(s, 4); 2.40(s, 6); 2.35(s, 6);                          2.10-1.40(br m, 24)                                            24    *        7.30(s, 4); 2.50(s, 12); 2.00(s, 24)                           25    >230     **                                                             26    >230     **                                                             27    145-150  7.50-7.40(m, 2); 7.30-7.10(m, 2); 2.67(br t, 2);                              2.07(br s, 12); 1.65(br q, 2); 1.36(br q, 2);                                 0.93(t, 3, J=7)                                                28    210-211  7.44(d, 4, J=8); 7.28(d, 4, J=8); 6.81(s, 8);                                 2.29(s, 12); 2.00(s, 24)                                       29    151-155  7.81(s, 2); 7.50(s, 1); 6.80(s, 8); 2.34(s, 12);                              2.01(s, 24); 0.19(s, 9)                                        30    210-211  7.47(s, 3); 6.72(s, 8); 3.79(br s, 1) 3.39(br s, 1);                          2,26(s, 12); 1.93(s, 24); 1.45(br s, 6); 0.98(br s, 6)         31    212-213  8.03(s, 2); 7.64(d, 2, J=8); 7.53(s, 1); 7.25(d, 2,                           J=8); 6.71(s, 8); 2.44(s, 3); 2.28(s, 12); 1.82(s, 24)         32    207-208  7.65(s, 2); 7.38(s, 1); 6.74(s, 8); 2.27(s, 12);                              1.93(s, 24)                                                    33    167-169  7.65(s, 2); 7.16(s, 1); 6.85(2s, 4); 2.35(2s, 12);                            2.03(s, 6); 2.02(s, 6); 1.95(s, 6); 1.94(s, 6)                 34    178-184  7.40(s, 3); 6.79(s, 6); 2.33(s, 18); 1.98(s, 18);                             1.89(s, 18)                                                    35    210-211  7.45-7.35(m, 3); 7.28(d, 2, J=7.5); 6.72(s, 8);                               6.66(s, 2); 2,57(s, 6); 2,24(s, 6);                                           2.06-1.87(numerous s, 42)                                      36    >230     7.79(br m, 2); 7.35(s, 2); 7.24-7.20(m, 2);                                   6.86(br d, 4); 2.36(s, 12); 2.30-1.70(br d, 24)                37    210-212  7.87-7.84(m, 2); 7.37(s, 2); 7.20-7.15(m, 2);                                 6.75(s, 8); 2.27(s, 12); 1.95(br s, 24)                        38    158-165  7.90(d, 1, J=2); 7.68(d, 1, J=9); 7.40(d, 1, J=7);                            7.37(d, 1, J=7); 7.24(dd, 1, J=9); 6.77(2s, 12);                              2.28(2s, 18); 1.95(br s, 36)                                   39    >250     7.64(d, 4, J=8); 7.55(d, 4, J=8); 6.92(s, 4); 2.39(s,                         12); 2.12(s, 12); 2.02(s, 12)                                  40    220-225  7.50(s, 3); 6.65(s, 12); 2.23(s, 18); 1.89(s,                  ______________________________________                                                       36)                                                             *the value was not determined                                                 **not measured since compounds insoluble                                 

II. Preparation of the Borates EXAMPLE 1b

Preparation of the tetramethylammonium butyl borate of the compound fromExample 1

Method F: 1 equivalent of butyllithium (0.015 mol) in hexane is added at0° C. over the course of 15 minutes to a stirred solution of 8.6 g(0.015 mol) of 1,4-bis(dimesitylboryl)benzene in 80 ml of THF. Thereaction mixture is allowed to warm to room temperature and is thenconcentrated in vacuo. The residue is treated with 80 ml of a mixture ofmethanol and water in a ratio of 4:1 and is filtered in order to removeunreacted bisborane. An excess of tetramethylammonium chloride is added,whereupon a white solid precipitates. Filtration and drying give 5.0 g(47% of theory) of the title product. Method G: The borate can also beobtained directly from the 1,4-dibromobenzene without isolating theintermediates, by method B. In this case, following the second warmingto room temperature, the reaction mixture is diluted with additional THFso as to give a homogeneous solution. The tetramethylammonium borate isthen obtained in a yield of 78% of theory accordance with method F.

Further Examples

The compounds of Examples 1a-h, 2a-f, 3a-d, 4a-h, 5a-c, 6a,7a-d, 8a-l,9a-b, 10a, 12a-d, 13a, 14a-b, 15a-f, 16a-c, 17a-b, 18a-b, 20a,23a, 24a,28a, 29a, 34a-b, 35a, 36a, 37a, 38a, 39a-d and 40a are given in Table 2,which also lists the respective preparation method and physical data.

                                      TABLE 2                                     __________________________________________________________________________    Borates                                                                           Borane                                                .sup.11 B-              Compd                                  Prepa-                                                                             Melting   NMR                     from                                                                              Type of               Equivalents  ration                                                                             range Yield                                                                             160 Hz              Ex. Ex. borate       Counterion                                                                             of base      method                                                                              °C.!                                                                         %! δ             __________________________________________________________________________                                                               ppm!               1a  1   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    #     78  -9.61               1b  1   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F, G 215-219                                                                             47;78                                                                             -8.35               1c  1   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    229-231                                                                             91  -8.71               1d  1   Butyl        Cyanin*  1 C.sub.4 H.sub.9 Li                                                                       F    102-111                                                                             87  -8.25               1e  1   Butyl        QTX**    1 C.sub.4 H.sub.9 Li                                                                       F    160-170                                                                             82  -8.52               1f  1   Phenyl       N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.6 H.sub.4 Li                                                                       F    >230  81  -5.96               1g  1   Phenyl       Cyanine* 1 C.sub.6 H.sub.4 Li                                                                       F    120-123                                                                             33  #                   1h  1   Diphenyl     2 N(CH.sub.3).sub.4.sup.+                                                              LiC.sub.6 H.sub.4 Li                                                                       F    >230  59  -1.96               2a  2   (CH.sub.3).sub.3 Si                                                                        N(CH.sub.3).sub.4.sup.+                                                                1 (CH.sub.3).sub.3 Si                                                                      F    130-170                                                                             80  -9.50                       CH.sub.2              CH.sub.2 Li                                     2b  2   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    128-132                                                                             77  -9.45               2c  2   s-Butyl      N(CH.sub.3).sub.4.sup.+                                                                1 s-C.sub.4 H.sub.9 Li                                                                     F    136-152                                                                             29  -6.57               2d  2   Benzyl       N(CH.sub.3).sub.4.sup.+                                                                1 BenzylLi   F    >250  89  -8.03               2e  2                                                                                  ##STR61##   Li.sup.+                                                                                ##STR62##   F    192-195                                                                             69  -10.21              2f  2                                                                                  ##STR63##   N(CH.sub.3).sub.4.sup.+                                                                 ##STR64##   F    140-142                                                                             85  -9.62               3a  3   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    170-172                                                                             100 -8.92                                                                         -9.76               3b  3   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    172-182                                                                             86  -7.38                                                                         -8.18               3c  3   Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    180-184                                                                             87  -8.72                                                                         -9.77               3d  3   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    224-225                                                                             22  -7.59                                                                         -8.61               4a  4   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    180-188                                                                             82  -8.60               4b  4   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    162-172                                                                             80  -7.40               4c  4   Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    179-180                                                                             98  -8.84               4d  4   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    230-232                                                                             61  -7.64               4e  4   Butyl        Cyanine* 1 C.sub.4 H.sub.9 Li                                                                       F    110-124                                                                             89  -7.64               4f  4   Butyl        QTX**    1 C.sub.4 H.sub.9 Li                                                                       F    154-161                                                                             84  -7.67               4g  4   Phenyl       N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.6 H.sub.5 Li                                                                       F    200-205                                                                             75  -5.20               4h  4   Phenyl       Cyanine* 1 C.sub.6 H.sub.5 Li                                                                       F    138-140                                                                             72  -5.23               5a  5   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    210-220                                                                             100 -9.62               5b  5   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    150-160                                                                             36  -8.73               5c  5   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    185-187                                                                             52  -8.16               6a  6   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    >230  86  -9.91               7a  7   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    138-140                                                                             25  -8.77                                                                         -9.72               7b  7   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    138-149                                                                             82  #                   7c  7   Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    223-233                                                                             69  -8.18                                                                         -9.28               7d  7   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    139-145                                                                             66  #                   8a  8   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    210-215                                                                             100 -9.63               8b  8   Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    172-184                                                                             65  -8.74               8c  8   Butyl        N(C.sub.4 H.sub.9)4.sup.+                                                              1 C.sub.4 H.sub.9 Li                                                                       F    78-80 53  -8.71               8d  8   Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    >270  71  -9.67               8e  8   Dimethyl     2 N(C.sub.4 H.sub.9).sup.+                                                             2 CH.sub.3 Li                                                                              F    159-160                                                                             69  -9.68               8f  8   Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    265-267                                                                             63  -8.46               8g  8   Dibutyl      2 N(C.sub.4 H.sub.9).sup.+                                                             2 C.sub.4 H.sub.9 Li                                                                       F    225-227                                                                             52  -8.82               8h  8   Butyl        Cyanine* 1 C.sub.4 H.sub.9 Li                                                                       F    105-109                                                                             60  -8.30               8i  8   Butyl        QTX**    1 C.sub.4 H.sub.9 Li                                                                       F    153-165                                                                             75  -8.30               8j  8   Phenyl       N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.6 H.sub.5 Li                                                                       F    >250  74  -6.23               8h  8   Butyl        Cyanine* 1 C.sub.4 H.sub.9 Li                                                                       F    105-109                                                                             60  -8.30               8k  8   Phenyl       Cyanine* 1 C.sub.6 H.sub.5 Li                                                                       F    147-157                                                                             63  -6.23               8l  8   Diphenyl     2 N(CH.sub.3).sub.4.sup.+                                                              LiC.sub.6 H.sub.5 Li                                                                       F    >230  39  -2.52               9a  9   Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    150-170                                                                             55  -9.06                                                                         -9.96               9b  9   Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    #     81  -9.08                                                                         -10.01              10a 10  Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    #     #   #                   12a 12  Methyl       N(C.sub.4 H.sub.9)4.sup.+                                                              1 CH.sub.3 Li                                                                              F    165-167                                                                             58  -9.99               12b 12  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    >230  58  -8.41               12c 12  Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    205-210                                                                             66  -8.77               12d 12  Butyl        Cyanine* C.sub.4 H.sub.9 Li                                                                         F    103-110                                                                             41  -8.35               13a 13  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    #     26  #                   14a 14  Methyl       N(CH.sub.3).sub.4.sup.+                                                                CH.sub.3 Li  F    160-180                                                                             62  -10.09              14b 14  Butyl        N(CH.sub.3).sub.4.sup.+                                                                C.sub.4 H.sub.9 Li                                                                         F    160-180                                                                             63  -8.84               15a 15  Methyl       N(CH.sub.3).sub.4.sup.+                                                                CH.sub.3 Li  F    230-235                                                                             86  -9.23               15b 15  Butyl        N(CH.sub.3).sub.4.sup.+                                                                C.sub.4 H.sub.9 Li                                                                         F    152-165                                                                             62  -7.35               15c 15  Dimethyl     2 N(CH.sub.3).sub.4.sup.+                                                              2 CH.sub.3 Li                                                                              F    >230  37  -8.82               15d 15  Dibutyl      2 N(CH.sub.3).sub.4.sup.+                                                              2 C.sub.4 H.sub.9 Li                                                                       F    168-173                                                                             23  -7.28               15e 15  Butyl        Cyanine* 1 C.sub.4 H.sub.9 Li                                                                       F    125-157                                                                             48  -7.40               15f 15  Butyl        QTX**    1 C.sub.4 H.sub.9 Li                                                                       F    146-156                                                                             38  -7.42               16a 16  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    149-157                                                                             80  -6.03               16b 16  Butyl        Cyanine* 1 C.sub.4 H.sub.9 Li                                                                       F    120-129                                                                             78  -6.23               16c 16  Butyl        QTX**    1 C.sub.4 H.sub.9 Li                                                                       F    146-152                                                                             81  -6.42               17a 17  Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    >230  26  -9.91               17b 17  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    230-232                                                                             47  -7.35               18a 18  Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    199-200                                                                             74  -7.83               18b 18  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    115-120                                                                             81  -7.18               20a 20  Butyl        N(CH.sub.3).sub.4.sup.+                                                                0.5 C.sub.4 H.sub.9 Li per                                                                 F    179-180                                                                             40  -8.62               . . .                         eq. of boron                                    23a 23  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    >220  57  #                   24a 24  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    141-142                                                                             15  #                   28a 28  Butyl        N(CH.sub.3).sub.4                                                                      1 C.sub.4 H.sub.9 Li                                                                       F    >250  81  -8.45               29a 29  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    125-130                                                                             74  -8.38               34a 34  Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    130-160                                                                             81  -9.16               34b 34  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    150-157                                                                             82  -7.69               35a 35  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    170-185                                                                             62  -8.55               36a 36  Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    186-190                                                                             35  -7.91               37a 37  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    152-155                                                                             31  #                   38a 38  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    145-150                                                                             43  -7.06               39a 39  Methyl       N(CH.sub.3).sub.4.sup.+                                                                1 CH.sub.3 Li                                                                              F    184-199                                                                             52  -8.72               39b 39  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    185-195                                                                             53  -7.55               39c 39  Phenyl       N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.6 H.sub.5 Li                                                                       F    227-230                                                                             64  #                   39d 39  Phenyl       Cyanine* 1 C.sub.6 H.sub.4 Li                                                                       F    153-167                                                                             52  -5.45               40a 40  Butyl        N(CH.sub.3).sub.4.sup.+                                                                1 C.sub.4 H.sub.9 Li                                                                       F    198-199                                                                             75  -8.82               __________________________________________________________________________     ##STR65##                                                                    -  -                                                                           ##STR66##                                                                    -  -                                                                           . . . the precise position of the butyl groups in the polyborate has not      been determined.   -                                                          # the values were not determined                                         

Ill. Use Examples EXAMPLE 41

Reactivity of the polyborates in a resist formulation

A photocurable formulation is prepared by mixing the followingcomponents:

10.0 g of dipentaerythritol monohydroxypentaacrylate, ®SR 399, SartomerCo., Berkshire, GB

15.0 g of tripropylene glycol diacrylate, Sartomer Co., Berkshire, GB

15.0 g of N-vinylpyrrolidone, Fluka

10.0 g of trimethylolpropane triacrylate, Degussa

50,0 g of urethane acrylate ®ACTYLAN AJ20, Societe Nationale des Poudreset Explosifs

0.3 g of levelling assistant ®BYK 300, BYK-Mallinckrodt

Portions of this composition are mixed with 0.4 or 1.6%, based on theoverall quantity of the formulation, of the novel polyboratephotoinitiator. All operations are carried out under red light. Thesamples to which polyborate has been added are applied to a 300 μmaluminium foil. The thickness of the dry film is 60 μm. To this filmthere is applied a 76 μm thick polyester film, over which a standardizedtest negative having 21 steps of different optical density (Stoufferwedge) is placed. The sample is covered with a second UV-transparentfilm and compressed on a metal plate by means of vacuum. Exposure iscarried out in a first test series for 5 seconds, in a second series for10 seconds and in a third series for 20 seconds, using a 4 kW xenon lampat a distance of 30 cm. Following exposure, the cover films and the maskare removed and the exposed film is developed in ethanol for 10 secondsat 23° C. in an ultrasound bath. Drying is carried out at 40° C. in aconvection oven for 5 minutes. The sensitivity of the initiator systemused is characterized by indicating the last wedge step which wasreproduced (i.e. polymerized) without tack. The higher the number ofsteps, the more sensitive the system tested. The results are summarizedin Table 3.

                  TABLE 3                                                         ______________________________________                                                               Number of steps reproduced                             Compound    Concentration                                                                            after exposure times of                                from Example                                                                               %!        5 s      10 s 20 s                                     ______________________________________                                        1a          0.4        2        4    7                                        1b          0.4        4        6    9                                        1c          0.4        3        5    8                                        3a          1.6        4        6    9                                        3b          1.6        5        7    10                                       4a          1.6        5        7    10                                       4b          0.4        5        7    9                                        4b          1.6        5        7    10                                       6a          1.6        2        4    7                                        8a          1.6        5        7    10                                       8b          1.6        7        9    12                                       8d          1.6        3        5    8                                        8f          1.6        6        8    11                                       8g          1.6        3        5    8                                        9a          1.6        6        8    11                                       9b          1.6        3        5    8                                        12b         1.6        3        5    8                                        12c         1.6        4        6    9                                        14a         1.6        2        5    8                                        14b         1.6        4        6    9                                        15a         1.6        5        7    9                                        15b         1.6        7        9    12                                       16a         1.6        8        10   13                                       17a         1.6        4        6    9                                        17b         1.6        6        9    12                                       18a         1.6        3        5    7                                        ______________________________________                                    

EXAMPLE 42

Reactivity of the polyborates in a resist formulation

1.6%, based on the total quantity of the formulation, of eachphotoinitiator to be tested was incorporated into a formulation asdescribed in Example 41. Sample preparation, exposure and developmentwere likewise carried out by a method similar to that described inExample 41, but exposure was for 20 seconds in each case. The resultsare listed in Table 4.

                  TABLE 4                                                         ______________________________________                                        Compound from                                                                            Concentration                                                                            Number of steps reproduced                              Example     %!        after exposure for 20 s                                 ______________________________________                                        8j         1.6         7                                                      13a        1.6        10                                                      20a        1.6         8                                                      28a        1.6        11                                                      34a        1.6         8                                                      36a        1.6        15                                                      38a        1.6        15                                                      39a        1.6        12                                                      39b        1.6        12                                                      39c        1.6         7                                                      23a        1.6        13                                                      ______________________________________                                    

EXAMPLE 43

Reactivity of the polyborates in combination with a dye in a resistformulation

A photocurable formulation is prepared by mixing the followingcomponents:

10.0 g of dipentaerythritol monohydroxypentaacrylate, ®SR 399, SartomerCo., Berkshire, GB

15.0 g of tripropylene glycol diacrylate, Sartomer Co., Berkshire, GB

15.0 g of N-vinylpyrrolidone, Fluka

10.0 g of trimethylolpropane triacrylate, Degussa

50.0 g of urethane acrylate ®ACTYLAN AJ20, Societe Nationale des Poudreset Explosifs

0.3 g of levelling assistant ®BYK 300, Byk-Mallinckrodt

Portions of this composition are mixed with 0.4%, based on the overallquantity of the formulation, of the novel polyborate photoinitiator and0.3% of the dye of the following structure: ##STR67##

All operations are carried out under red light. The samples to whichpolyborate has been added are applied to a 300 μm aluminium foil. Thethickness of the dry film is 60 μm. To this film there is applied a 76μm thick polyester film, over which a standardized test negative having21 steps of different optical density (Stouffer wedge) is placed. Thesample is covered with a second UV-transparent film and compressed on ametal plate by means of vacuum. Exposure is carried out in a first testseries for 5 seconds, in a second series for 10 seconds and in a thirdseries for 20 seconds, using a 4 kW xenon lamp at a distance of 30 cm.Following exposure, the cover films and the mask are removed and theexposed film is developed in ethanol for 10 seconds at 23° C. in anultrasound bath. Drying is carried out at 40° C. in a convection ovenfor 5 minutes. The sensitivity of the initiator system used ischaracterized by indicating the last wedge step which was reproduced(i.e. polymerized) without tack. The higher the number of steps, themore sensitive the system tested. The results are summarized in Table 5.

                  TABLE 5                                                         ______________________________________                                                     Number of steps reproduced after                                 Compound     exposure times of                                                from Example 5s           10s   20s                                           ______________________________________                                        1a           11           13    16                                            1b           11           13    17                                            3a           10           12    15                                            3b           11           13    16                                            4a            9           11    14                                            4b           10           12    15                                            6a            7           13    17                                            8b           13           16    19                                            8f           12           14    17                                            8g           13           15    21                                            9a           11           13    16                                            9b           10           15    16                                            12b           9           12    15                                            12c          16           18    20                                            14a           9           14    17                                            14b           4            7    20                                            15a          14           17    20                                            15b          14           17    20                                            17a          11           16    18                                            17b          14           17    20                                            ______________________________________                                    

EXAMPLE 44

Reactivity of the polyborates in combination with a dye in a resistformulation

0.4%, based on the total quantity of the formulation, of eachphotoinitiator to be tested and 0.3% of the dye described in Example 43was incorporated into a formulation as described in Example 43. Samplepreparation, exposure and development were likewise carried out by amethod similar to that described in Example 43, but exposure was for 20seconds in each case. The results are listed in Table 6.

                  TABLE 6                                                         ______________________________________                                        Compound from                                                                              Number of steps reproduced                                                                     Bleaching                                       Example      after 20 s       behaviour                                       ______________________________________                                        2b           13               --                                              2c           14               --                                              2d           14               --                                              13a          17               b                                               20a          17               b                                               28a          17               b                                               29a          17               b                                               34a          12               --                                              34b          12               --                                              35a          15               b                                               36a          17               b                                               38a          18               b                                               39a          17               b                                               39b          17               b                                               40a          16               b                                               23a          18               b                                               ______________________________________                                         *b = bleaches out (visual examination)                                        --= bleaching out is not observed; however, this does not mean that it        does not occur, but denotes only that it is not noted in the course of        visual examination                                                       

EXAMPLE 45

Reactivity of dye-polyborate salts in a resist formulation

The novel dye-polyborate salts are incorporated in a concentration of0.3%, based on the overall quantity of the formulation, into aformulation as described in Example 41. In these compounds the dyefunctions as a countercation to the polyborate anion. The compoundscontain the dye cations F⁺ or Q⁺ : ##STR68##

Preparation and curing of the samples are likewise carried out asdescribed in Example 41. The results are listed in Table 7.

                  TABLE 7                                                         ______________________________________                                                            Number                                                    Compound            of steps reproduced                                       from                after exposure times of                                                                     Bleaching                                   Example   Cation    5 s   10 s   20 s behaviour                               ______________________________________                                        1d        F.sup.+   12    15     16   b                                       4e        F.sup.+    9    12     15   --                                      8h        F.sup.+   12    14     17   --                                      12d       F.sup.+   11    14     17   b                                       15e       F.sup.+   13    15     18   b                                       16b       F.sup.+   11    13     16   --                                      1e        Q.sup.+    8    10     12   --                                      4f        Q.sup.+    7     9     12   --                                      8i        Q.sup.+    8    10     12   --                                      15f       Q.sup.+    8    10     12   --                                      16c       Q.sup.+    7     9     11   --                                      ______________________________________                                         *b = bleaches out (visual examination)                                        *= bleaching out is not observed; however, this does not mean that it doe     not occur, but denotes only that it is not noted in the course of visual      examination                                                              

EXAMPLE 46

Reactivity of dye-polyborate salts in a resist formulation

The procedure of Example 45 is repeated but the exposure time is 20seconds. The results are given in Table 8.

                  TABLE 8                                                         ______________________________________                                        Compound from  Number of steps                                                Example        reproduced                                                     ______________________________________                                        1g             11                                                             4h              9                                                             8k             12                                                             39d             8                                                             ______________________________________                                    

EXAMPLE 47

Reactivity of polyborates in combination with electron acceptors

A formulation is prepared as described in Example 43. Portions of thecomposition are mixed with 0.4% of the photoinitiator to be tested andwith 0.3% of a substance A, B, C, D or E. ##STR69##

The samples are prepared and cured likewise in a manner similar to thatdescribed in Example 43. The results are given in Table 9.

                  TABLE 9                                                         ______________________________________                                        Compound             Number of steps reproduced after                         from         Electron                                                                              exposure times of                                        Example      acceptor                                                                              5 s       10 s 20 s                                      ______________________________________                                         4b          A       5         7    10                                        15a          A       5         7     9                                         4b          B       6         8    10                                        15a          B       4         6     9                                         4b          C       5         7    10                                        15a          C       4         6     8                                         4b          D       5         7    10                                        15a          D       5         7    10                                         4b          E       7         9    12                                        15a          E       7         9    11                                        ______________________________________                                    

EXAMPLE 48

Polyboranes as electron acceptors in a resist formulation

A formulation is prepared as described in Example 43. Portions of thecomposition are mixed with 0.4% of tetramethylammonium triphenyl butylborate and 0.3% of a polyborane of the present application. The samplesare prepared and cured likewise in a manner similar to that described inExample 43. The results are given in Table 10.

                  TABLE 10                                                        ______________________________________                                        Compound   Number of steps reproduced                                         from       after exposure times of                                            Example    5 s          10 s   20 s                                           ______________________________________                                        1          1            3      7                                              8          3            6      9                                              ______________________________________                                    

EXAMPLE 49

Polyboranes as electron acceptors in a resist formulation

A formulation is prepared as described in Example 43. Portions of thecomposition are mixed with 2% of the compound from Example 1 and with1.5% of an electron donor. The samples are prepared and cured likewisein a manner similar to that described in Example 43. The results aregiven in Table 11.

                  TABLE 11                                                        ______________________________________                                                        Number of steps reproduced after                              Electron donor  exposure for 20 s                                             ______________________________________                                        N-Methyldiethanolamine                                                                        5                                                             Triphenylphosphine                                                                            3                                                             2,5-            2                                                             Diisopropyldimethylaniline                                                    ______________________________________                                    

EXAMPLE 50

Combinations of polyborates with monoborates

A photocurable composition is prepared by mixing the followingcomponents:

    ______________________________________                                        37.64 g       of ® Sartomer SR 444, pentaerythritol triacrylate,                        (Sartomer Company, Westchester)                                 10.76 g       of ® CYMEL 301, hexamethoxymethylmelamine                                 (American Cyanamid, USA)                                        47.30 g       of ® CARBOSET 525, thermoplastic polyacrylate                             containing carboxyl groups (B.F. Goodrich)                      4.30  g       of polyvinylpyrrolidone PVP (GAF, USA)                          100.00                                                                              g       of this composition are mixed with                              319.00                                                                              g       of methylene chloride and                                       30.00 g       of methanol.                                                    ______________________________________                                    

Samples of this composition are mixed with in each case 0.68% of a novelpolyborate and 0.68% of tetramethylammonium N-butyl triphenyl borate,based on the solids content, by stirring at room temperature for onehour. All operations are carried out under red light. The samples towhich initiator has been added are applied to a 300 μm aluminium foil(10×15 cm). The solvent is removed by first drying at room temperaturefor 5 minutes and then heating at 60° C. for 15 minutes in a convectionoven, to give a dry film thickness of 35 μm. A 76 μm thick polyesterfilm is placed on the liquid film, and a standardized test negative with21 steps of different optical density (Stouffer wedge) is placed overthis. The sample is covered with a second UV-transparent film and iscompressed on a metal plate by means of vacuum. The sample is thenexposed for 40 seconds using a 4 kW xenon lamp at a distance of 30 cm.After exposure, the cover films and the mask are removed and the exposedfilm is developed for 240 seconds with 1% strength aqueous sodiumcarbonate solution in an ultrasound bath and then dried at 60° C. in aconvection oven for 15 minutes. The sensitivity of the initiator systemused is characterized by indicating the last wedge step reproducedwithout tack. The higher the number of steps, the more sensitive thesystem. An increase by two steps denotes an approximate doubling of thecuring rate. The results are given in Table 12.

                  TABLE 12                                                        ______________________________________                                        Compound from                                                                 Example      Number of steps reproduced                                       ______________________________________                                        39a          11                                                                8b           8                                                               ______________________________________                                    

EXAMPLE 51

Combinations of dye-borate salts with polyboranes

A photocurable composition is prepared by mixing the followingcomponents:

    ______________________________________                                        37.64 g       of ® Sartomer SR 444, pentaerythritol triacrylate,                        (Sartomer Company, Westchester)                                 10.76 g       of ® CYMEL 301, hexamethoxymethylmelamine                                 (American Cyanamid, USA)                                        47.30 g       of ® CARBOSET 525, thermoplastic polyacrylate                             containing carboxyl groups (B.F. Goodrich)                      4.30  g       of polyvinylpyrrolidone PVP (GAF, USA)                          100.00                                                                              g       of this composition are mixed with                              319.00                                                                              g       of methylene chloride and                                       30.00 g       of methanol.                                                    ______________________________________                                    

Samples of this composition are mixed with in each case 0.3% of a novelpolyborane and 0.3% of the following dye-borate salt, based on thesolids content, by stirring at room temperature for one hour. ##STR70##

All operations are carried out under red light. The samples to whichinitiator has been added are applied to a 300 μm aluminium foil (10×15cm). The solvent is removed by first drying at room temperature for 5minutes and then heating at 60° C. for 15 minutes in a convection oven,to give a dry film thickness of 35 μm. A 76 μm thick polyester film isplaced on the liquid film, and a standardized test negative with 21steps of different optical density (Stouffer wedge) is placed over this.The sample is covered with a second UV-transparent film and iscompressed on a metal plate by means of vacuum. The sample is thenexposed for 40 seconds using a 4 kW xenon lamp at a distance of 30 cm.After exposure, the cover films and the mask are removed and the exposedfilm is developed for 240 seconds with 1% strength aqueous sodiumcarbonate solution in an ultrasound bath and then dried at 60° C. in aconvection oven for 15 minutes. The sensitivity of the initiator systemused is characterized by indicating the last wedge step reproducedwithout tack. The higher the number of steps, the more sensitive thesystem. An increase by two steps denotes an approximate doubling of thecuring rate. The results are given in Table 13.

                  TABLE 13                                                        ______________________________________                                        Compound from Example                                                                         Number of steps reproduced                                    ______________________________________                                        8               17                                                            ______________________________________                                    

EXAMPLE 52

Dye-polyborate salts in a resist formulation with a Ar⁺ laser as lightsource

The novel dye-polyborate salts are incorporated in a concentration of0.3%, based on the overall quantity of the formulation, into aformulation as described in Example 41. The dye functions as acounterion to the polyborate anion and corresponds to the dye cation F(see Example 45). Sample preparation and development are as described inExample 41, but exposure is carried out using a Ar⁺ laser (UNIPHASE1583, beam diameter 0.65 mm, divergence 0.95 mrad) with monochromaticlight of wavelength 488 nm and an output of 20 mW. The laser beam, witha diameter of about 2.5 mm, is moved at a rate of 24 mm/s over a 21-stepStouffer wedge which is fixed to the sample. After development, a linevarying in width and length is left. For evaluation, the number of stepsis indicated at which a cured line can still be seen. The results aregiven in Table 14.

                  TABLE 14                                                        ______________________________________                                        Compound                     Bleaching                                        from Example                                                                              Number of steps reproduced                                                                     behaviour.sup.*                                  ______________________________________                                        15e         8                b                                                8h          9                --                                               1d          9                b                                                12d         10               b                                                ______________________________________                                         .sup.* b = bleaches out (visual examination)   = bleaching out is not         observed; however, this does not mean that it does not occur, but denotes     only that it is not noted in the course of visual examination            

EXAMPLE 53

Combinations of dyes with polyborates in a resist formulation using aAr⁺ laser as light source

0.4% of the novel polyborate salt and 0.3% of the dye from Example 43,based on the overall quantity of the formulation, are incorporated intoa formulation as described in Example 41. Sample preparation, exposure,development and evaluation are as described in Example 52. The resultsare given in Table 15.

                  TABLE 15                                                        ______________________________________                                        Compound from                Bleaching                                        Example     Number of steps reproduced                                                                     behaviour.sup.*                                  ______________________________________                                        12c         11               b                                                ______________________________________                                         .sup.* b = bleaches out (visual examination)                             

EXAMPLE 54

Combinations of dyes with polyborates in a resist formulation with afrequency-doubled Nd/YAG laser as light source

The novel dye-polyborate salts are incorporated in a concentration of0.3%, based on the overall quantity of the formulation, into aformulation as described in Example 41. The dye functions as acounterion to the polyborate anion and corresponds to the dye cation F(see Example 45). Sample preparation and development are as described inExample 41, but exposure is carried out using a frequency-doubled Nd/YAGlaser (COHERENT DPSS 532-50, beam diameter 0.7 mm, divergence <1.3 mrad)with monochromatic light of wavelength 532 nm and an output of 50 mW.The laser beam, with a diameter of about 3.3 mm, is moved at a rate of 6mm/s over a 21-step Stouffer wedge which is fixed to the sample. Afterdevelopment, a line varying in width and length is left. For evaluation,the number of steps is indicated at which a cured line can still beseen. The results are given in Table 16.

                  TABLE 16                                                        ______________________________________                                        Compound from                Bleaching                                        Example     Number of steps reproduced                                                                     behaviour.sup.*                                  ______________________________________                                        15e         13               b                                                8h          13               --                                               1d          12               b                                                12d         12               b                                                ______________________________________                                         .sup.* b = bleaches out (visual examination)   = bleaching out is not         observed; however, this does not mean that it does not occur, but denotes     only that it is not noted in the course of visual examination            

EXAMPLE 55

Combinations of dyes with polyborates in a resist formulation using afrequency-doubled Nd/YAG laser as light source

The novel polyborate salt from Example 12c in a concentration of 0.4%,and 0.3% of the dye from Example 43, based on the overall quantity ofthe formulation, are incorporated into a formulation as described InExample 41. Sample preparation, exposure, development and evaluation areas described in Example 53. The results are given in Table 17.

                  TABLE 17                                                        ______________________________________                                        Compound from Example                                                                         Number of steps reproduced                                    ______________________________________                                        12c             12                                                            ______________________________________                                    

EXAMPLE 56

Polyborates as thermal initiators

0.3% of the novel polyborates was added to the formulation described inExample 41, and about 15 mg thereof were weighed into DSC boats (underred light). The exothermy of the curing reaction was then determined ata heating rate of 10 degrees per minute using a Mettler DSC 30. Theinitial temperature (T_(A)) and peak temperature (T_(P)) of theexotherms were determined. Those initiators for which the initial orpeak temperature lies below the values for the pure formulation arethermal initiators. The results are summarized in Table 18.

                  TABLE 18                                                        ______________________________________                                        Compound         T.sub.A  °C.!                                                                  T.sub.P  °C.!                                 ______________________________________                                        Formulation      135     145                                                  38a              110     120                                                  ______________________________________                                    

EXAMPLE 57

Polyborates in combination with electron acceptors as thermal initiators

0.3% of the novel polyborates and 0.4% of the electron acceptor A ofexample 47 were added to the formulation described in Example 41, andabout 10 mg thereof were weighed into DSC boats (under red light). Theexothermy of the curing reaction was then determined at a heating rateof 10 degrees per minute using a Mettler DSC 30. The initial temperature(T_(A)) and peak temperature (T_(P)) of the exotherms were determined.Those initiators for which the initial or peak temperature lies belowthe values for the pure formulation are thermal initiators. The resultsare summarized in Table 19.

                  TABLE 19                                                        ______________________________________                                        Compound  Electron acceptors                                                                            T.sub.A  °C.!                                                                  T.sub.P  °C.!                        ______________________________________                                        Formulation                                                                             --              135     145                                         38a       A               113     127                                         36a       A               110     --                                          ______________________________________                                    

What is claimed is:
 1. A compound of the formula I ##STR71## in which nand o are each a number from 0 to 50; m is a number from 1 to 50;u and vare 0 or 1, and at least one of the indices u and v is 1; R₁, R₂,R_(2a), R₃ and R₄ independently of one another are phenyl or anotheraromatic hydrocarbon, which radicals are unsubstituted or aresubstituted by unsubstituted or halo-, OR₆ - and/or NR₈ R₉ -substitutedC₁ -C₆ alkyl, OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉,C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen; p is 0, 1or 2; q is 0 or 1; R₅ is C₁ -C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, C₂ -C₈alkenyl, phenyl-C₁ -C₆ alkyl or naphthyl-C₁ -C₃ the radicals C₁ -C₁₂alkyl, C₃ -C₁₂ cycloalkyl, C₂ -C₈ alkenyl, phenyl-C₁ -C₆ alkyl ornaphthyl being unsubstituted or substituted by OR₆, S(O)_(p) R₇, OS(O)₂R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, ##STR72## SiR₁₁ R₁₂ R₁₃, BR₁₄R₁₅ or halogen, or R₅ is phenyl or another aromatic hydrocarbon radical,which radicals are unsubstituted or substituted by C₁ -C₆ alkyl, OR₆,S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂R₁₃, BR₁₄ R₁₅ or halogen, at least one of the radicals R₁, R₂, R_(2a),R₃, R₄ and R₅ being a phenyl radical which is substituted ortho to thebond to the boron atom, or being another aromatic hydrocarbon radicalwhich is sterically hindered ortho to the boron atom; R₆ and R₇ areunsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- or halo-substituted C₁-C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆ alkyl-, --C₁ -C₁₂alkoxy- or -halo-substituted phenyl, or unsubstituted or mono- topenta-C₁ -C₆ alkyl-, --C₁ -C₁₂ alkoxy- or -halo-substituted phenyl-C₁-C₆ alkyl; R_(7a) is C₁ -C₁₂ alkyl R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ andR₁₅ independently of one another are as defined for R₆ or are C₃ -C₁₂cycloalkyl, or R₈ and R₉, together with the N atom to which they areattached, form a 5- or 6-membered ring which may additionally contain Oor S atoms, or R₁₄ and R₁₅, together with the B atom to which they areattached, form a 5- or 6-membered ring; X is C₁ -C₂₀ alkylene which isunsubstituted or substituted by OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉,C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅, halogen orP(O)_(q) R₁₆ R₁₇, or X is C₃ -C₁₂ cycloalkylene or C₂ -C₈ alkenylene,each of which is unsubstituted or substituted by OR₆, S(O)_(p) R₇,OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅or halogen, or where these radicals are interrupted by one or moregroups --O--, --S(O)_(p) -- or --NR₁₈ --, or X is a divalent aromatichydrocarbon radical which is unsubstituted or substituted by C₁ -C₆alkyl, OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉,C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ or halogen, or X is C₁ -C₂₀ alkylenewhich is interrupted by one or more groups --O--, --S(O)_(p) -- or--NR₁₈ --, or X is a radical of the formula II or III ##STR73## R₁₆ andR₁₇ independently of one another are as defined for R₆ or are C₃ -C₁₂cycloalkyl, R₁₈ is as defined for R₆ or is hydrogen; Y is --(CH₂)_(r)--, --C(O)--, --NR₁₈ --, --O--, --S(O)_(p) --, --CR₁₉ R₂₀ --, ##STR74##r is 1, 2 or 3; s is 2 or 3; R₁₉ and R₂₀ are C₁ -C₆ alkyl or phenyl, orR₁₉ and R₂₀, together with the C atom to which they are attached, form a5- or 6-membered ring; A and Q independently of one another are a directbond, --(CH₂)_(r) --, --CH═CH--, --C(O)--, --NR₁₈ --, --S(O)_(p) --,--CR₁₉ R₂₀ --, ##STR75## or the radicals R₁, R₂, R₃, R₄ and X formbridges to produce radicals of the formula (IV) or (V) ##STR76## G is--(CH₂)_(t) --, --CHCH--, --C(O)--, --NR₁₈ --, --O--, --S(O)_(p) --,--CR₁₉ R₂₀ --, ##STR77## t is 0, 1 or 2; the radicals of the formulae(II), (III), (IV) and (V) being unsubstituted or being substituted onthe aromatic rings by OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆,C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ or halogen and whereadditional phenyl rings may be fused to the phenyl rings of the formulae(II), (III), (IV) and (V); provided that R₁, R_(2a), R₃ and R₄ are notsimultaneously α-naphthyl, if X is phenylene or 4,4'-biphenylene; and Zis a radical which is able to form positive ions.
 2. A compoundaccording to claim 1, in which n and o are zero.
 3. A compound accordingto claim 2, in which m is
 1. 4. A compound according to claim 1, inwhich R₁, R_(2a), R₃ and R₄ are identical.
 5. A compound according toclaim 1, in which R₁, R_(2a), R₂, R₃, R₄, R₁₄ and R₁₅ independently ofone another are 2-, 2,6- or 2,4,6-substituted phenyl or are naphthyl oranthracyl.
 6. A compound according to claim 5, in which R₁, R_(2a), R₂,R₃, R₄, R₁₄ and R₁₅ are C₁ -C₆ alkyl-, halo-, OR₆ - ortrifluoromethyl-substituted phenyl, 1-naphthyl, 1- or 9-anthracyl.
 7. Acompound according to claim 1, in which X is C₁ -C₁₈ alkylene which isunsubstituted or substituted by OR₆, NR₈ R₉, SiR₁₁ R₁₂ R₁₃, BR₁₄ R₁₅ orhalogen, or in which X is C₁ -C₂₀ alkylene which is interrupted by oneor more groups --O--, or in which X is phenylene, biphenylene, o-, m- orp-terphenylene, naphthylene, phenanthrylene or ferrocenylene, where theradicals phenylene, biphenylene, o-, m- or p-terphenylene, naphthylene,phenanthrylene or ferrocenylene are unsubstituted or substituted by C₁-C₆ alkyl, OR₆, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃,BR₁₄ R₁₅ or halogen, or in which X is a radical o formula II in whichYis --(CH₂)_(r) --, --C(O)--, --N--, --O--, --S(O)_(p) --, --CR₁₉ R₂₀ --,##STR78##
 8. A compound according to claim 1, in whichn and o are both0, m is the number 1, R₁, R_(2a), R₂, R₃ and R₄ are phenyl substitutedby C₁ -C₆ alkyl and/or halogen, R₅ is C₁ -C₁₂ alkyl, (C₁ -C₄ alkyl)₃Si--CH₂ -- or phenyl, X is unsubstituted phenylene, halo-substituted,biphenylene, o- or p-terphenylene, naphthylene, phenanthrylene,ferrocenylene or a radical of the formula II in which Y is --C(O)-- or##STR79## s is 2, and Z is tetraalkylammonium, a cyanine-dye cation or athioxanthon cation.
 9. A composition comprising(a) at least oneethylenically unsaturated photopolymerizable compound and (b) at leastone compound of the formula I as defined in claim
 1. 10. A compositionaccording to claim 9 comprising in addition to components (a) and (b) atleast one coinitiator or electron acceptor (c).
 11. A compositionaccording to claim 10, in which the electron acceptor (c) is a dye. 12.A composition according to claim 10, in which the electron acceptor (c)is an ultraviolet absorber.
 13. A composition according to claim 12, inwhich the ultraviolet absorber is a thioxanthone derivative, coumarine,benzophenone, a benzophenone derivative or a hexaarylbisimidazolederivative.
 14. A composition according to claim 9, comprising inaddition to components (a) and (b) at least one compound of the formulaXI ##STR80## in which R_(a), R_(b), R_(c) and R_(d) independently of oneanother are C₁ -C₁₂ alkyl, trimethylsilylmethyl, phenyl, anotheraromatic hydrocarbon, C₁ -C₆ alkylphenyl, allyl, phenyl-C₁ -C₆ alkyl, C₂-C₈ alkenyl, C₂ -C₈ alkynyl, C₃ -C₁₂ cycloalkyl or saturated orunsaturated heterocyclic radicals, wherein the radicals phenyl, anotheraromatic hydrocarbon, phenyl-C₁ -C₆ alkyl and saturated or unsaturatedheterocyclic radical ar unsubstituted or substituted by unsubstituted orhalo-, OR₆ - and/or NR₈ R₉ -substituted C₁ -C₆ alkyl, OR₆, S(O)_(p) R₇,OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁ R₁₂ R₁₃, BR₁₄R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen;p is 0, 1 or 2; q is 0 or 1; R₆ and R₇are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- or halo-substitutedC₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆ alkyl-, --C₁ -C₁₂alkoxy- or -halo-substituted phenyl, or unsubstituted or mono- topenta-C₁ -C₆ alkyl-, --C₁ -C₁₂ alkoxy- or -halo-substituted phenyl-C₁-C₆ alkyl; R_(7a) is C₁ -C₁₂ alkyl; R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ andR₁₅ independently of one another are as defined for R₆ or are C₃ -C₁₂cycloalkyl, or R₈ and R₉, together with the N atom to which they areattached, form a 5- or 6-membered ring which may additionally contain Oor S atoms, or R₁₄ and R₁₅, together with the B atom to which they areattached, form a 5- or 6-membered ring; R₁₆ and R₁₇ independently of oneanother are as defined for R₆ or are C₃ -C₁₂ cycloalkyl; and E is aradical which is able to form positive ions.
 15. A composition accordingto 9, comprising in addition to component (b) a further photoinitiator(d) and/or other additives.
 16. A composition according to claim 9,comprising in addition to components (a) and (b) at least one neutral,anionic or cationic dye or a thioxanthone compound and an oniumcompound.
 17. A composition according to claim 16, additionallycomprising a free-radical photoinitiator.
 18. A composition according toclaim 16, additionally comprising an α-amino ketone compound.
 19. Acomposition according to claim 9, comprising at least one borate of theformula I and at least one dye which changes or loses its colour duringor after irradiation, which dye may also, as a cation, be part of thecompound of the formula I.
 20. A composition according to claim 9,containing from 0.05 to 15% by weight, of component (b), based on thecomposition.
 21. A coated substrate which is coated on at least onesurface with a composition according to claim
 9. 22. A compositioncomprising(a) at least one ethylenically unsaturated photopolymerizablecompound and (b) at least one polyborate anion of the formula Ia##STR81## in which the radicals R₁, R₂, R_(2a), R₃, R₄, R₅ and X, andalso n, m, o, u and v, are as defined in claim 1, and (c) a dye cation,sulfonium- or iodonium cation.
 23. A composition according to claim 22,additionally comprising at least one further borate compound of theformula XI ##STR82## in which R_(a), R_(b), R_(c) and R_(d)independently of one another are C₁ -C₁₂ alkyl, trimethylsilylmethyl,phenyl, another aromatic hydrocarbon, C₁ -C₆ alkylphenyl, allyl,phenyl-C₁ -C₆ alkyl, C₂ -C₈ alkenyl, C₂ -C₈ alkynyl, C₃ -C₁₂ cycloalkylor saturated or unsaturated heterocyclic radicals, wherein the radicalsphenyl, another aromatic hydrocarbon, phenyl-C₁ -C₆ alkyl and saturatedor unsaturated heterocyclic radical ar unsubstituted or substituted byunsubstituted or halo-, OR₆ - and/or NR₈ R₉ -substituted C₁ -C₆ alkyl,OR₆, S(O)_(p) R₇, OS(O)₂ R₇, NR₈ R₉, C(O)OR₆, C(O)NR₈ R₉, C(O)R₁₀, SiR₁₁R₁₂ R₁₃, BR₁₄ R₁₅, P(O)_(q) R₁₆ R₁₇ or halogen;p is 0, 1 or 2; q is 0 or1; R₆ and R₇ are unsubstituted or COOR_(7a), OH, C₁ -C₁₂ alkoxy- orhalo-substituted C₁ -C₁₂ alkyl, unsubstituted or mono- to penta-C₁ -C₆alkyl-, --C₁ -C₁₂ alkoxy- or -halo-substituted phenyl, or unsubstitutedor mono- to penta-C₁ -C₆ alkyl-, --C₁ -C₁₂ alkoxy- or -halo-substitutedphenyl-C₁ -C₆ alkyl; R_(7a) is C₁ -C₁₂ alkyl; R₈, R₉, R₁₀, R₁₁, R₁₂,R₁₃, R₁₄ and R₁₅ independently of one another are as defined for R₆ orare C₃ -C₁₂ cycloalkyl, or R₈ and R₉, together with the N atom to whichthey are attached, form a 5- or 6-membered ring which may additionallycontain O or S atoms, or R₁₄ and R₁₅, together with the B atom to whichthey are attached, form a 5- or 6-membered ring; R₁₆ and R₁₇independently of one another are as defined for R₆ or are C₃ -C₁₂cycloalkyl; and E is a radical which is able to form positive ions. 24.A photoinitiator comprising at least one compound of the formula Iaccording to claim 1 and at least one electron acceptor compound.
 25. Aprocess for the photopolymerization of nonvolatile monomeric, oligomericor polymeric compounds containing at least one ethylenically unsaturateddouble bond, which comprises adding at least one compound of the formulaI according to claim 1 to said compounds and irradiating the resultingcomposition with light having a wavelength ranging from 200 nm up to andincluding the infrared region.
 26. A process according to claim 25wherein the composition to be irradiated is a pigmented or nonpigmentedpaint or varnish, a powder coating, a printing ink, a printing plate, anadhesive, a dental composition, a color proofing system, a glass fibercable coating, a screen printing stencil, a resist material, a compositecomposition, an encapsulation for electrical and electronic components,a magnetic recording material, an image recording material, a waveguide,an optical switch for photographic reproduction or a three-dimensionalobject.
 27. A process for the thermal polymerization of compoundscontaining ethylenically unsaturated double bonds, which comprisesadding as polymerization initiator at least one compound of the formula1 according to claim 1 and heating the resulting composition to effect athermal polymerization.